Magnesium-containing carrier components and application thereof to olefin polymerization

ABSTRACT

Solid fine particles which contain a magnesium atom, an aluminum atom and a C 1-20  alkoxy group simultaneously, are insoluble in a hydrocarbon solvent, and have an average particle diameter of 3 to 80 μm, and an olefin polymerization catalyst containing the solid fine particles and a transition metal compound in the groups 3 to 11 in the periodic table, exhibit a very high olefin polymerization activity without combination with an expensive organoaluminum oxy compound or organoboron compound and maintains a high activity in polymerization for a long time, and an olefin polymer excellent in powdery properties can be produced by using the olefin polymerization catalyst. The transition metal compound in the groups 3 to 11 in the periodic table includes a transition metal compound having a ligand containing two or more atoms selected from a boron atom, a nitrogen atom, an oxygen atom, a phosphorus atom and a sulfur atom.

TECHNICAL FIELD

The present invention relates to an olefin polymerization catalyst and aprocess for producing an olefin polymer by using the olefinpolymerization catalyst and in particular to an olefin polymerizationcatalyst not containing an organoaluminum oxy compound or an organoboroncompound used conventionally as an olefin polymerization catalystcomponent, a process for producing an olefin polymer by using the olefinpolymerization catalyst, and polyolefins excellent in powdery propertiesobtained by this process.

BACKGROUND ART

There is known a method of polymerizing an olefin wherein a metallocenecompound having a group having conjugated π electrons particularlycyclopentadiene and its derivative as a ligand is used as a catalyst tobe combined with an organoaluminum oxy compound or an organoboroncompound. For example, JP-A 58-19309 discloses a method of polymerizingan olefin wherein bicyclopentadienyl zirconium dichloride and methylaluminoxane are used as a catalyst. Recently, a system wherein olefinpolymerization proceeds without using combination with an organoaluminumoxy compound or an organoboron compound is also disclosed. For example,JP-A 4-211405 discloses a method of polymerizing an olefin by using acombination of a zirconium metallocene compound and a solid carrierobtained by contacting magnesium chloride and an active hydrogen-freeelectron donor with active hydrogen-containing electron donor. Further,JP-A 7-330821 discloses a method of polymerizing an olefin by using acombination of a titanium metallocene compound and a solid componentobtained by reacting a magnesium compound such as magnesium halide withan organoaluminum compound.

However, a majority of known methods including the method of JP-A58-19309 suffer from a problem that the metallocene compound when usedwithout combination with an expensive organoaluminum oxy compound ororganoboron compound cannot exhibit a high olefin polymerizationactivity. Even if the metallocene compound exhibits a high olefinpolymerization activity by combination with an expensive organoaluminumoxy compound or organoboron compound, the duration of the activity wasoften short. Further, the bulk density of a formed polymer afterpolymerization is low to make handling difficult, and when suchcatalysts are applied to a gaseous phase or liquid phase polymerizationmethod, the resulting polymer adheres to a polymerizer wall thusdeteriorating heat transfer to make cooling difficult and to permitformation of polymer agglomerates, and thus there are many problems tobe solved in process in order to use such catalysts in producingpolyolefin in an industrial scale.

In recently disclosed methods of permitting olefin polymerization toproceed without combination with an organoaluminum oxy compound or anorganoboron compound, on one hand, there still remain many features tobe improved from an economical point of view and from the viewpoint oflarge-scale production. In JP-A 4-211405 supra, for example, dibutylmagnesium which is expensive and unstable in the air should be used as astarting material in order to regulate the particle diameter ofmagnesium chloride as a carrier, and in JP-A 7-330821 supra, expensiveand unstable diethoxy magnesium is used as a carrier. It is hardly saidthat these known techniques not using combination with an organoaluminumoxy compound or an organoboron compound are satisfactory in respect ofthe polymerization activity, the powdery properties of a formed polymer,and molecular weight characteristics such as molecular-weightdistribution etc.

DISCLOSURE OF INVENTION

The present invention was made in view of the technical backgrounddescribed above, and the object of the present invention is to provide apolymerization catalyst exhibiting a high olefin polymerization activitywithout combination with an expensive organoaluminum oxy compound ororganoboron compound and maintaining a high activity in polymerizationfor a long time, as well as a process for producing olefin polymersexcellent in powdery properties by using the catalyst. This object isachieved by using an olefin polymerization catalyst containing solidfine particles prepared by a specific method, which contain a magnesiumatom, an aluminum atom and a C₁₋₂₀ alkoxy group simultaneously, satisfythe requirements (i) the molar ratio of magnesium atom to aluminum atom(Mg/Al) is in the range of 1.0<(Mg/Al)≦300.0, (ii) the molar ratio ofalkoxy group to aluminum atom (OR/Al) is in the range of0.5<(OR/Al)<2.0, and (iii) the average particle diameter is in the rangeof 3 to 80 μm, and are insoluble in a hydrocarbon solvent.

BEST MODE FOR CARRYING OUT THE INVENTION

The present invention relates to 1) a carrier component containingmagnesium, 2) an olefin polymerization catalyst containing the carriercomponent, 3) a method of polymerizing an olefin by using the olefinpolymerization catalyst, and 4) polyolefin obtained by thispolymerization method. Hereinafter, the means to solve the problem ineach item is described in detail.

Carrier Component Containing Magnesium

The carrier component containing magnesium in the present invention(hereinafter abbreviated sometimes to “carrier”) is characterized bycontaining a magnesium atom, an aluminum atom and a C₁₋₂₀ alkoxy groupsimultaneously, being insoluble in a hydrocarbon solvent, and having anaverage particle diameter of 3 to 80 μm. The molar ratio of magnesiumatom to aluminum atom (Mg/Al) in the carrier component is in the rangeof 1.0<Mg/Al≦300.0, and the molar ratio of alkoxy group to aluminum atom(OR/Al) is 0.05<OR/Al<2.0.

The phrase “being insoluble in a hydrocarbon solvent” means that asoluble part of magnesium atoms is 0.5 weight % or less under stirringin at least one solvent selected from hexane, decane and toluene for 1minute to 1 hour under atmospheric pressure in the temperature range of0° C. to the inherent boiling point of the solvent, and also thatsoluble parts of aluminum atoms and alkoxy groups are each 1 weight % orless under stirring in at least one solvent selected from hexane, decaneand toluene for 1 minute to 1 hour under atmospheric pressure at roomtemperature.

The carrier component of the present invention may contain other metalatoms and other organic groups than magnesium, aluminum and an alkoxygroup, but is preferably free of a transition metal atom in the group 4,such as titanium, zirconium and hafnium. For example, when a titaniumatom is contained in the carrier component of the present invention, anolefin polymer derived from compound (A) described later, that is, atransition metal compound in the groups 3 to 11 in the periodic table,having a ligand containing two or more atoms selected from a boron atom,a nitrogen atom, an oxygen atom, a phosphorus atom and a sulfur atom,and an olefin polymer derived from a titanium atom contained therein,are simultaneously formed, and thus the primary structure of theresulting polymer is hardly controlled. For the reason described above,it is preferable that the carrier component of the present invention isfree of a transition metal atom in the group 4 and simultaneously doessubstantially not exhibit an olefin polymerization activity incombination with optionally used component (C) described later.

The total amount of a magnesium atom, an aluminum atom and a C₁₋₂₀alkoxy group contained in the carrier component of the present inventionis usually in the range of 10 to 90 weight %, preferably in the range of15 to 60 weight %, particularly preferably 20 to 40 weight %, from theviewpoint of the polyolefin polymerization activity of a carriercomponent-containing polymerization catalyst described later and thepowdery properties of polyolefin obtained as a result of polymerization.The largest component other than the magnesium atom, aluminum atom andC₁₋₂₀ alkoxy group contained in the carrier component is a halogen atom.When the halogen atom is a chlorine atom, the amount of chlorine atom inthe carrier component ranges from about 20 weight % at the minimum toabout 80 weight % at the maximum. In addition, an alcohol correspondingto the C₁₋₂₀ alkoxy group or a remaining organic solvent etc. used atthe time of preparing the carrier component may be contained in thecarrier component.

The C₁₋₂₀ alkoxy group in the carrier component of the present inventionis a group derived from a C₁₋₂₀ alcohol used as a starting component atthe time of preparing the carrier component as described later. TheC₁₋₂₀ alkoxy group includes a methoxy group, ethoxy group, n-propoxygroup, i-propoxy group, n-butoxy group, i-butoxy group, t-butoxy group,n-pentoxy group, i-amyloxy group, n-hexoxy group, n-heptoxy group,2-ethylhexoxy group, n-octoxy group, dodecoxy group, octadecyloxy group,oleyloxy group, benzyloxy group, phenylethoxy group, cumyloxy group,i-propylbenzyloxy group etc., a halogen-containing alkoxy group such astrichloromethoxy group, trichloroethoxy group, trichlorohexoxy groupetc., and a lower alkyl-containing phenoxy group such as phenoxy group,cresoxy group, ethylphenoxy group, nonylphenoxy group, cumylphenoxygroup, naphthoxy group etc., among which a methoxy group, ethoxy group,propoxy group, butoxy group, pentoxy group, i-amyloxy group, hexoxygroup, heptoxy group, 2-ethylhexoxy group, octoxy group, dodecoxy groupetc. are preferable.

The molar ratio of magnesium atom to aluminum atom (Mg/Al) in thecarrier component of the present invention is usually in the range of1.0<Mg/Al≦300.0, preferably 30.0<Mg/Al≦250.0, more preferably30.0<Mg/Al≦200.0, still more preferably 35.0<Mg/Al≦200.0, further morepreferably 40.0<Mg/Al≦150.0, from the viewpoint of olefin polymerizationactivity and the powdery properties of formed polyolefin. The molarratio of alkoxy group to aluminum atom (OR/Al) is usually in the rangeof 0.05<OR/Al<2.0, preferably 0.1≦OR/Al<1.8, more preferably0.2≦OR/Al<1.0, in further increasing the olefin polymerization activity.

When the carrier component of the present invention having an averageparticle diameter of 3 to 80 μm, preferably 3 to 50 μm, is used as anolefin polymerization catalyst described later, the polymerizationactivity is improved while the bulk density of formed polyolefin can beincreased. In the carrier component of the present invention, aparameter which is important similarly to the parameter of averageparticle diameter is crystallite size determined by X-ray diffractionanalysis of magnesium halide constituting the carrier component. Thiscrystallite size is highly correlated with the polymerization activity,and a carrier component having a small crystallite size is considerednecessary to achieve a high polymerization activity. However, when thecrystallite size is extremely small, the polymerization activity ishigh, but deterioration of the particle morphology of the catalystcomponent is estimated. Accordingly, the crystallite size in the presentinvention is usually 3 to 80 (Å), preferably 10 to 75 (Å), morepreferably 12 to 70 (Å), still more preferably 15 to 60 (Å), furthermore preferably 20 to 55 (Å).

The carrier component of the present invention is obtained by contactinga magnesium halide with a C₁₋₂₀ alcohol (hereinafter, this contact isreferred to sometimes as “first contact”) and then contacting theproduct with an organoaluminum compound represented by the followinggeneral formula (Z) (

) (hereinafter, this contact is referred to sometimes as “secondcontact”), but the method of preparing the carrier component of thepresent invention is not limited to this preparation method.

As the magnesium halide, magnesium chloride and magnesium bromide arepreferably used. As the magnesium halide, a commercial product may beused as it is, or the magnesium halide may be prepared separately fromalkyl magnesium and the magnesium halide thus prepared can also be usedwithout isolation.

The C₁₋₂₀ alcohol includes alcohols corresponding to the above-mentionedC₁₋₂₀ alkoxy groups, and examples thereof include methanol, ethanol,n-propanol, i-propanol, n-butanol, i-butanol, t-butanol, n-pentanol,i-amyl alcohol, n-hexanol, n-heptanol, 2-ethyl hexanol, n-octanol,dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethanol, cumyl alcohol, i-propylbenzyl alcohol etc., ahalogen-containing alcohol such as trichloromethanol, trichloroethanol,trichlorohexanol etc., and phenol or lower alkyl-containing phenol suchas cresol, ethyl phenol, nonyl phenol, cumyl phenol, naphthol etc.,among which methanol, ethanol, propanol, butanol, pentanol, i-amylalcohol, hexanol, heptanol, 2-ethyl hexanol, octanol and dodecanol arepreferable.

The magnesium halide may be contacted with the C₁₋₂₀ alcohol in thepresence of a solvent. The solvent includes aliphatic hydrocarbons suchas hexane, heptane, octane, decane, dodecane and kerosene; alicyclichydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane etc.;aromatic hydrocarbons such as benzene, toluene, xylene etc.; halogenatedhydrocarbons such as ethylene dichloride, chlorobenzene, dichloromethaneetc., or mixtures thereof.

Contact is carried out usually under heating. In heating, a temperatureup to the boiling point of the solvent used can be arbitrarily selected.The contact time is varied depending on contact temperature, and forexample, under conditions where n-decane is used as solvent and theheating temperature is 130° C., there appears a phenomenon where thereaction mixture is made uniform by contact for about 4 hours, which isindicative of completion of contact. Contact is carried out usually byusing a unit facilitating contact under stirring etc. When the contactis initiated, the system is usually heterogeneous, but as the contactproceeds, the reaction mixture is made gradually uniform and finallyliquefied. Regardless of the degree of liquefaction, the carriercomponent of the present invention is useful as a component of theolefin polymerization catalyst, but is prepared preferably via a processinvolving complete liquefaction, from the viewpoint of the olefinpolymerization activity and the powdery properties of the formedpolyolefin.

The thus prepared contact product of the magnesium halide and C₁₋₂₀alcohol (hereinafter referred to sometimes as “first contact product)may be used without distilling the solvent away or after removal of thesolvent etc. used at the time of contact. Usually, the product issubjected to the subsequent step without distilling the solvent away.

The first contact product obtained by the above method is then contacted(=second contact) with an organoaluminum compound represented by thefollowing general formula (Z):AlR_(n)X_(3-n)  (Z)

In the general formula (Z), R represents a C₁₋₂₀ hydrocarbon group,specifically a methyl group, ethyl group, propyl group, butyl group,hexyl group, octyl group and decyl group. X represents a halogen atomsuch as a chlorine atom, bromine atom etc. or a hydrogen atom. n is aninteger of 1 to 3, preferably 2 or 3. When there are a plurality of Rs,the Rs may be the same or different, and when there are a plurality ofXs, the Xs may be the same or different. Specifically, the followingcompounds are used as the organoaluminum compound. The organoaluminumcompound meeting such requirements includes trialkyl aluminum such astrimethyl aluminum, triethyl aluminum, triisopropyl aluminum,triisobutyl aluminum, trioctyl aluminum, tri-2-ethylhexyl aluminum etc.;alkenyl aluminum such as isoprenyl aluminum etc.; dialkyl aluminumhalide such as dimethyl aluminum chloride, diethyl aluminum chloride,diisopropyl aluminum chloride, diisobutyl aluminum chloride, dimethylaluminum bromide etc.; alkyl aluminum sesquihalide such as methylaluminum sesquichloride, ethyl aluminum sesquichloride, isopropylaluminum sesquichloride, butyl aluminum sesquichloride, ethyl aluminumsesquibromide etc.; alkyl aluminum dihalide such as methyl aluminumdichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride,ethyl aluminum dibromide etc.; and alkyl aluminum hydride such asdiethyl aluminum hydride, diisobutyl aluminum hydride etc., among whichtrimethyl aluminum, triethyl aluminum, triisobutyl aluminum, trihexylaluminum, trioctyl aluminum, diethyl aluminum chloride, ethyl aluminumsesquichloride, ethyl aluminum dichloride and diisobutyl aluminumhydride are preferable.

The contact method for the second contact is not particularly limited,but usually the second contact is carried out by a method of adding theorganoaluminum compound represented by the general formula (Z) to thefirst contact product under stirring. In this step, the first contactproduct may have been diluted with a solvent, and as the solvent, ahydrocarbon not having active hydrogen can be used without particularlimitation, but usually the second contact can be carried outefficiently by using, as the solvent in the second contact, the solventused in the first contact without distilling it away. The organoaluminumcompound added to the first contact product may be used after dilutionwith a solvent, or may be added without dilution with a solvent, butusually the organoaluminum compound is used in a form diluted with analiphatic saturated hydrocarbon such as n-decane and n-hexane or anaromatic hydrocarbon solvent such as toluene and xylene. When theorganoaluminum compound is added, the compound is added to the firstcontact product usually over 5 minutes to 5 hours. When coolingperformance in the catalytic system is sufficient, it can be added for ashort time, and when the performance is insufficient, it is addedpreferably for a long time. The organoaluminum compound may be added allat once or several times in divided portions. When added in dividedportions, the organoaluminum compounds in divided portions may be thesame or different, and the temperature of the first contact product upondivided addition may be the same or different.

The organoaluminum compound represented by the general formula (Z) isused such that the molar ratio of the organoaluminum compound in thesecond contact to the magnesium atom in the first contact product isusually 0.1 to 50, preferably 0.5 to 30, more preferably 1.0 to 20,still more preferably 1.5 to 15, further still more preferably 2.0 to10.

In the method of preparing the carrier by the second contact, aparticularly preferable mode of the second contact is described below.

In contacting the first contact product with the organoaluminum compoundrepresented by the general formula (Z) above, it is preferable that, forexample, a hydrocarbon dilution of the magnesium compound is contactedwith a hydrocarbon dilution of the organoaluminum compound so that boththe dilutions are reacted. Usually, the molar ratio of theorganoaluminum compound to the magnesium compound is varied depending onits type and contact conditions, but is preferably 2 to 10. The shapeand size of the solid product is varied depending on its formingconditions. To obtain a solid product having a regulated shape andparticle diameter, it is preferably to avoid rapid formation, and forexample, when the magnesium compound and the organoaluminum compound,both in a liquid form, are contacted and mixed with each other to form asolid product by mutual reaction, it is preferable that the two arecontacted and mixed at a low temperature so as to prevent rapidformation of solids, followed by increasing the temperature to form asolid product gradually. According to this method, it is easy toregulate the particle diameter of the solid product, and a granular orspherical solid product having a narrow particle size distribution canbe easily obtained.

A polymer obtained by slurry polymerization or gaseous phasepolymerization using the thus obtained granular or spherical carriercomponent excellent in particle size distribution is granular orspherical, has narrow particle-size distribution and high bulk density,and is excellent in flowability.

The carrier component described above is not only useful as aconstitutional component of the olefin polymerization catalyst describedlater but is also utilizable as a catalyst for many organic synthesisreactions by virtue of the functions of Lewis acid contained in thecarrier component.

Olefin Polymerization Catalyst Containing the Carrier Component

The olefin polymerization catalyst of the present invention contains thecarrier component described above. The polymerization catalyst includesan olefin polymerization catalyst comprising:

(A) a transition metal compound in the groups 3 to 11, having a ligandcontaining two or more atoms selected from a boron atom, a nitrogenatom, an oxygen atom, a phosphorus atom and a sulfur atom,

(B) the carrier component described above, and if necessary

(C) a specific organometallic compound.

The transition metal compound (A) in the groups 3 to 11, having a ligandcontaining two or more atoms selected from a boron atom, a nitrogenatom, an oxygen atom, a phosphorus atom and a sulfur atom may be carried(and is carried more preferably from the viewpoint of the powderyproperties of a formed olefin polymer) on the carrier component (B).

The transition metal compound (A) in the groups 3 to 11, having a ligandcontaining two or more atoms selected from a boron atom, a nitrogenatom, an oxygen atom, a phosphorus atom and a sulfur atom, used in thepresent invention, includes for example compounds (a-1) to (a-27)described below. These transition metal compounds may be used alone oras a mixture of two or more thereof.

Compound (a-1)

As the component (A) in the present invention, compound (a-1)represented by the following general formulae (I) to (III) can be used.

wherein N . . . M¹, N . . . M² and N . . . M³ generally show that thetwo elements are coordinated, but in the present invention, they may ormay not be coordinated.

M¹ in formula (I), M² in formula (II) and M³ in formula (II) may be thesame or different and each represent a transition metal atom selectedfrom the groups 3 to 11 in the periodic table (the group 3 alsocontaining lanthanoids), preferably a transition metal atom in thegroups 3 to 6 and 8 to 10, more preferably a transition metal atom inthe group 4, 5 or 6, still more preferably a metal atom in the group 4or 5. Examples thereof include scandium, titanium, zirconium, hafnium,vanadium, niobium, tantalum, cobalt, rhodium, yttrium, chromium,molybdenum, tungsten, manganese, rhenium, iron, ruthenium, nickel,palladium etc., preferably scandium, titanium, zirconium, hafnium,vanadium, niobium, tantalum, iron, cobalt, rhodium, nickel, palladiumetc., more preferably titanium, zirconium, hafnium, vanadium, niobium,tantalum, chromium, molybdenum etc., still more preferably titanium,zirconium, hafnium, vanadium, niobium, tantalum etc. m in formula (I),m′ in formula (II) and m″ in formula (III) may be the same or differentand each represent an integer of 1 to 6, preferably an integer of 1 to4, more preferably an integer of 1 to 3, still more preferably aninteger of 1 to 2.

k in formula (I), k′ in formula (II) and k″ in formula (III) may be thesame or different and each represent an integer of 1 to 6, preferably aninteger of 1 to 4, more preferably an integer of 1 to 3, still morepreferably an integer of 1 to 2.

In formula (I), A represents an oxygen atom, a sulfur atom or asubstituent —R⁶-containing nitrogen atom (—N(R⁶)—), preferably an oxygenatom or a nitrogen atom.

In formula (I), D represents a nitrogen atom, a phosphorus atom or asubstituent —R⁷-containing carbon atom (—N(R⁷)—), preferably asubstituent —R⁷-containing carbon atom.

In formula (I), R¹ to R⁷ may be the same or different and each representa hydrogen atom, a halogen atom, a hydrocarbon group, anoxygen-containing group, a nitrogen-containing group, a boron-containinggroup, a sulfur-containing group, a phosphorus-containing group, aheterocyclic compound residue, a silicon-containing group, agermanium-containing group or a tin-containing group, and two or more ofthese groups may be bound to one another to form a ring.

In formula (II), G represents an oxygen atom, a sulfur atom or asubstituent —R¹²-containing nitrogen atom (—N(R¹²)—) preferably anoxygen atom.

In formula (II), E represents N-binding —R¹³ and —R¹⁴, or ═C(R¹⁵)R¹⁶.

In formula (II), R⁸ to R¹⁶ may be the same or different and eachrepresent a hydrogen atom, a halogen atom, a hydrocarbon group, anoxygen-containing group, a nitrogen-containing group, a boron-containinggroup, a sulfur-containing group, a phosphorus-containing group, aheterocyclic compound residue, a silicon-containing group, agermanium-containing group or a tin-containing group, and two or more ofthese groups may be bound to one another to form a ring.

In formula (III), J represents a nitrogen atom, a phosphorus atom or asubstituent —R¹⁸-containing carbon atom (—C(R¹⁸)═), preferably asubstituent —R¹⁸-containing carbon atom.

In formula (III), T represents a nitrogen atom or a phosphorus atom,preferably a nitrogen atom.

In formula (III), L represents a nitrogen atom, a phosphorus atom or asubstituent —R¹⁹-containing carbon atom (—C(R¹⁹)═), preferably asubstituent —R¹⁹-containing carbon atom.

In formula (III), Q represents a nitrogen atom, a phosphorus atom or asubstituent —R²⁰-containing carbon atom (—C(R²⁰)═), preferably asubstituent —R²⁰-containing carbon atom.

In formula (III), R represents a nitrogen atom, a phosphorus atom or asubstituent —R²¹-containing carbon atom (—C(R²¹)═), preferably asubstituent —R²¹-containing carbon atom.

In formula (III), R¹⁷ to R²¹ may be the same or different and eachrepresent a hydrogen atom, a halogen atom, a hydrocarbon group, anoxygen-containing group, a nitrogen-containing group, a boron-containinggroup, a sulfur-containing group, a phosphorus-containing group, aheterocyclic compound residue, a silicon-containing group, agermanium-containing group or a tin-containing group, and two or more ofthese groups may be bound to one another to form a ring.

When m in formula (I) is 2 or more, R¹s, R²s, R³s, R⁴s, R⁵s, R⁶s or R⁷smay be the same or different. When m is 2 or more, two groups out of thegroups represented by R¹ to R⁷ may be bound to each other.

When m′ in formula (II) is 2 or more, R⁸s, R⁹s, R¹⁰s, R¹¹s, R¹²s, R¹³s,R¹⁴s, R¹⁵s or R¹⁶s may be the same or different. When p is 2 or more,two groups out of the groups represented by R⁸ to R¹⁶ may be bound toeach other.

When m″ in formula (III) is 2 or more, R¹⁷ s, R¹⁸s, R¹⁹s, R²⁰s or R²¹smay be the same or different. When r is 2 or more, two groups out of thegroups represented by R¹⁷ to R²¹ may be bound to each other.

The halogen atom represented by R¹ to R⁷ in formula (I), R⁸ to R¹⁶ informula (II) and R¹⁷ to R²¹ in formula (III) includes fluorine,chlorine, bromine and iodine.

Specific examples of the hydrocarbon group represented by R¹ to R⁷ informula (I) R⁸ to R¹⁶ in formula (II) and R¹⁷ to R²¹ in formula (III)include a C₁₋₃₀, preferably C₁₋₂₀, linear or branched alkyl group suchas methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl,tert-butyl, neopentyl, n-hexyl etc.;

a C₂₋₃₀, preferably C₂₋₂₀, linear or branched alkenyl group such asvinyl, allyl, isopropenyl etc.;

a C₂₋₃₀, preferably C₂₋₂₀, linear or branched alkynyl group such asethynyl, propargyl etc.;

a C₃₋₃₀, preferably C₃₋₂₀, saturated cyclic hydrocarbon group such ascyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamanthyl etc.;

a C₅₋₃₀ unsaturated cyclic hydrocarbon group such as cyclopentadienyl,indenyl, fluorenyl etc.;

a C₆₋₃₀, preferably C₆₋₂₀, aryl group such as phenyl, benzyl, naphthyl,biphenylyl, terphenylyl, phenanthryl, anthryl etc.; and

an alkyl-substituted aryl group such as methylphenyl, isopropylphenyl,t-butylphenyl, dimethylphenyl, diisopropylphenyl, di-t-butylphenyl,trimethylphenyl, triisopropylphenyl, tri-t-butylphenyl etc.

The hydrocarbon group may be the one whose hydrogen atom is replaced bya halogen, and examples thereof include a C₁₋₃₀, preferably C₁₋₂₀,halogenated hydrocarbon group such as trifluoromethyl,pentafluorophenyl, chlorophenyl etc.

The hydrocarbon group may be substituted with other hydrocarbon groups,and examples thereof include an alkyl group substituted with an arylgroup such as benzyl, cumyl etc.

The hydrocarbon group may be substituted with a heterocyclic compoundresidue; an oxygen-containing group such as an alkoxy group, aryloxygroup, ester group, ether group, acyl group, carboxyl group, carbonategroup, hydroxy group, peroxy group, carboxylic anhydride group etc.; anitrogen-containing group such as an amino group, imino group, amidegroup, imido group, hydrazino group, hydrazono group, nitro group,nitroso group, cyano group, isocyano group, cyanate group, amidinogroup, diazo group, a group whose amino group is converted into anammonium salt, etc.; a boron-containing group such as a borane diylgroup, borane triyl group, diboranyl group etc.; a sulfur-containinggroup such as a mercapto group, thioester group, dithioester group,alkylthio group, arylthio group, thioacyl group, thioether group,thiocyanate group, isothiocyanate group, sulfone ester group,sulfonamide group, thiocarboxyl group, dithiocarboxyl group, sulfogroup, sulfonyl group, sulfinyl group, sulphenyl group etc.; aphosphorus-containing group such as a phosphide group, phosphoryl group,thiophosphoryl group, phosphate group etc.; and a silicon-containinggroup, a germanium-containing group or a tin-containing group.

As described above, the hydrocarbon group may be substituted with anoxygen-containing group, a nitrogen-containing group, a boron-containinggroup, a sulfur-containing group, a phosphorus-containing group, asilicon-containing group, a germanium-containing group, a tin-containinggroup etc., and in this case, it is desired that an atomic groupcharacterizing a substituent group such as an oxygen-containing groupdoes not bind directly to a carbon atom in N or D in formula (I), acarbon atom in E in formula (II) and a carbon atom in J, L, Q, T or R informula (III).

Particularly preferable among these are a C₁₋₃₀, preferably C₁₋₂₀,linear or branched alkyl group such as methyl, ethyl, n-propyl,isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, neopentyl, n-hexyletc.; a C₆₋₃₀, preferably C₆₋₂₀, aryl group such as phenyl, naphthyl,biphenylyl, terphenylyl, phenanthryl, anthryl etc.; and a substitutedaryl group substituted with 1 to 5 substituent atoms or groups such as ahalogen atom, a C₁₋₃₀, preferably C₁₋₂₀, alkyl group or alkoxy group, aC₆₋₃₀, preferably C₆₋₂₀, aryl group or aryloxy group.

Two or more groups of R¹ to R⁷, preferably adjacent groups, may be boundto each other to form a ring; two or more groups of R⁸ to R¹⁶,preferably adjacent groups, may be bound to each other to form a ring;two or more groups of R¹⁷ to R²¹, preferably adjacent groups, may bebound to each other to form a ring. The ring includes, for example,condensed-ring groups such as a benzene ring, naphthalene ring,acenaphthene ring, indene ring etc., wherein a hydrogen atom on thecondensed ring may be replaced by an alkyl group such as methyl, ethyl,propyl or butyl.

The oxygen-containing group represented by R¹ to R⁷ in formula (I), R⁸to R¹⁶ in formula (II) and R¹⁷ to R²¹ in formula (III) is a groupcontaining 1 to 5 oxygen atoms, and does not include a heterocycliccompound residue described later. The oxygen-containing group does notinclude a group containing a nitrogen atom, a sulfur atom, a phosphorusatom, a halogen atom or a silicon atom having an oxygen atom bounddirectly thereto. Examples of the oxygen-containing group include, forexample, an alkoxy group, aryloxy group, ester group, ether group, acylgroup, carboxyl group, carbonate group, hydroxy group, peroxy group,carboxylic anhydride group etc., among which an alkoxy group, aryloxygroup, acetoxy group, carbonyl group, hydroxy group etc. are preferable.When the oxygen-containing group contains carbon atoms, it is desiredthat the number of carbon atoms is in the range of 1 to 30, preferably 1to 20.

The nitrogen-containing group represented by R¹ to R⁷ in formula (I), R⁸to R¹⁶ in formula (II) and R¹⁷ to R²¹ in formula (III) is a groupcontaining 1 to 5 nitrogen atoms, and does not include a heterocycliccompound residue described later. Examples of the nitrogen-containinggroup include, for example, an amino group, imino group, amide group,imido group, hydrazino group, hydrazono group, nitro group, nitrosogroup, cyano group, isocyano group, cyanate group, amidino group, diazogroup, a group whose amino group is converted into an ammonium salt,etc., preferably an amino group, imino group, amide group, imido group,nitro group, cyano group etc. When the nitrogen-containing groupcontains carbon atoms, it is desired that the number of carbon atoms is1 to 30, preferably 1 to 20.

The boron-containing group represented by R¹ to R⁷ in formula (I), R⁸ toR¹′ in formula (II) and R¹⁷ to R²¹ in formula (III) is a groupcontaining 1 to 5 boron atoms, and does not include a heterocycliccompound residue described later. Examples of the boron-containing groupinclude, for example, boron-containing groups such as a borane diylgroup, borane triyl group, diboranyl group etc., preferably a borylgroup substituted with one or two of C₁₋₃₀, preferably C₁₋₂₀,hydrocarbon groups or a borate group substituted with one to three ofthe hydrocarbon groups. When the group is substituted with two or morehydrocarbon groups, the hydrocarbon groups may be the same or different.

The sulfur-containing group represented by R¹ to R⁷ in formula (I), R⁸to R¹⁶ in formula (II) and R¹⁷ to R²¹ in formula (III) is a groupcontaining 1 to 5 sulfur atoms, and does not include a heterocycliccompound residue described later. Examples of the sulfur-containinggroup include, for example, a mercapto group, thioester group,dithioester group, alkylthio group, arylthio group, thioacyl group,thioether group, thiocyanate group, isothiocyanate group, sulfone estergroup, sulfonamide group, thiocarboxyl group, dithiocarboxyl group,sulfo group, sulfonyl group, sulfinyl group, sulphenyl group, sulfonategroup and sulfinate group, among which a sulfonate group, sulfinategroup, alkylthio group and arylthio group are preferable. When thesulfur-containing group contains carbon groups, it is desired that thenumber of carbon atoms is in the range of 1 to 30, preferably 1 to 20.

The phosphorus-containing group represented by R¹ to R⁷ in formula (I),R⁸ to R¹⁶ in formula (II) and R¹⁷ to R²¹ in formula (III) is a groupcontaining 1 to 5 phosphorus atoms, and does not include a heterocycliccompound residue described later. Examples of the phosphorus-containinggroup include, for example, a phosphino group, phosphoryl group,phosphothioyl group, phosphono group etc.

The heterocyclic compound residue represented by R¹ to R⁷ in formula(I), R⁸ to R¹⁶ in formula (II) and R¹⁷ to R²¹ in formula (III) is acyclic group containing 1 to 5 heteroatoms, and the heteroatom includesO, N, S, P and B. The cycle includes, for example, a 4- to 7-memberredmonocycle and multi-cycle, preferably a 5- to 6-memberred monocycle andmulti-cycle. Specifically, mention is made of for example anitrogen-containing compound residue such as pyrrole, pyridine,pyrimidine, quinoline, triazine etc.; an oxygen-containing compoundresidue such as furan, pyran etc.; and a sulfur-containing compoundresidue such as thiophene etc., and these groups may be furthersubstituted with a substituent group such as a C₁₋₃₀, preferably C₁₋₂₀,alkyl group or a C₁₋₃₀, preferably C₁₋₂₀, alkoxy group.

The silicon-containing group represented by R¹ to R⁷ in formula (I), R⁸to R¹⁶ in formula (II) and R¹⁷ to R²¹ in formula (III) is a groupcontaining 1 to 5 silicon atoms, and examples thereof include a silylgroup such as a hydrocarbon-substituted silyl group and a siloxy groupsuch as a hydrocarbon-substituted siloxy group. Specific examplesinclude methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl,diethylsilyl, triethylsilyl, diphenylmethylsilyl, triphenylsilyl,dimethylphenylsilyl, dimethyl-t-butylsilyl,dimethyl(pentafluorophenyl)silyl etc. Among these, methylsilyl,dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl,dimethylphenylsilyl, triphenylsilyl etc. are preferable, andtrimethylsilyl, triethylsilyl, triphenylsilyl, dimethylphenylsilyl etc.are particularly preferable. The hydrocarbon-substituted siloxy group isspecifically trimethylsiloxy etc. When the silicon-containing groupcontains carbon atoms, it is desired that the number of carbon atoms isin the range of 1 to 30, preferably 1 to 20.

The germanium-containing group and tin-containing group represented byR¹ to R⁷ in formula (I), R⁸ to R¹⁶ in formula (II) and R¹⁷ to R²¹ informula (III) include groups wherein in the silicon-containing groupsilicon is replaced by germanium or tin.

Examples of R¹ to R⁷ in formula (I), R⁸ to R¹⁶ in formula (II) and R¹⁷to R²¹ in formula (III) described above are described in more detail.

Preferable examples of the oxygen-containing group include an alkoxygroup such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy,isobutoxy, tert-butoxy etc., an aryloxy group such as phenoxy,2,6-dimethylphenoxy, 2,4,6-trimethylphenoxy etc., an acyl group such asformyl, acetyl, benzoyl, p-chlorobenzoyl, p-methoxybenzoyl etc., and anester group such as acetyloxy, benzoyloxy, methoxycarbonyl,phenoxycarbonyl, p-chlorophenoxycarbonyl etc.

Preferable examples of the nitrogen-containing group include analkylamino group such as methylamino, dimethylamino, diethylamino,dipropylamino, dibutylamino, dicyclohexylamino etc., an arylamino groupor alkylarylamino group such as phenylamino, diphenylamino,ditolylamino, dinaphthylamino, methylphenylamino etc., an imino groupsuch as methylimino, ethylimino, propylimino, butylimino, phenyliminoetc., anamide group such as acetamide, N-methylacetamide,N-methylbenzamide etc., and an imido group such as acetimido, benzimidoetc.

Preferable examples of the sulfur-containing group include an alkylthiogroup such as methylthio, ethylthio etc., an arylthio group such asphenylthio, methylphenylthio, naphthylthio etc., a thioester group suchas acetylthio, benzoylthio, methylthiocarbonyl, phenylthiocarbonyl etc.,a sulfone ester group such as methyl sulfonate, ethyl sulfonate, phenylsulfonate etc., and a sulfonamide group such as phenylsulfonamide,N-methylsulfonamide, N-methyl-p-toluenesulfonamide etc.

The sulfonate group includes methyl sulfonate, trifluoromethanesulfonate, phenyl sulfonate, benzyl sulfonate, p-toluene sulfonate,trimethyl benzene sulfonate, triisobutyl benzene sulfonate,p-chlorobenzene sulfonate, pentafluorobenzene sulfonate etc., and thesulfinate group includes methyl sulfinate, phenyl sulfinate, benzylsulfinate, p-toluene sulfinate, trimethyl benzene sulfinate,pentafluorobenzene sulfinate etc.

The phosphorus-containing group includes a phosphino group such asdimethyl phosphino, diphenyl phosphino etc., a phosphoryl group such asmethyl phosphoryl, isopropylphosphoryl, phenylphosphoryl etc., aphosphothioyl group such as methylphosphothioyl, isopropylphosphothioyl,phenylphosphothioyl etc., a phosphono group for example a phosphategroup and a phosphoric acid group such as dimethyl phosphate,diisopropyl phosphate, diphenyl phosphate etc.

In formula (I), n is a number satisfying the valence of M¹, and isspecifically an integer of 0 to 5, preferably 0 to 4, more preferably 0to 3.

In formula (II), q is a number satisfying the valence of M², and isspecifically an integer of 0 to 5, preferably 0 to 4, more preferably 0to 3.

In formula (III), r is a number satisfying the valence of M³, and isspecifically an integer of 0 to 5, preferably 0 to 4, more preferably 0to 3.

When X¹ in formula (I) is an atom or a group other than oxygen atom, nis preferably an integer of 1 to 4, more preferably 1 to 3.

When X² in formula (II) is an atom or a group other than oxygen atom, qis preferably an integer of 1 to 4, more preferably 1 to 3.

When X³ in formula (III) is an atom or a group other than oxygen atom, ris preferably an integer of 1 to 4, more preferably 1 to 3.

In formula (I), X¹ represents an atom or a group selected arbitrarilyfrom a hydrogen atom, a halogen atom, an oxygen atom, a hydrocarbongroup, an oxygen-containing group, a nitrogen-containing group, aboron-containing group, a sulfur-containing group, aphosphorus-containing group, a halogen-containing group, a heterocycliccompound residue, a silicon-containing group, an aluminum-containinggroup, a germanium-containing group and a tin-containing group.

In formula (II), X² represents an atom or a group selected arbitrarilyfrom a hydrogen atom, a halogen atom, an oxygen atom, a hydrocarbongroup, an oxygen-containing group, a nitrogen-containing group, aboron-containing group, a sulfur-containing group, aphosphorus-containing group, a halogen-containing group, a heterocycliccompound residue, a silicon-containing group, an aluminum-containinggroup, a germanium-containing group and a tin-containing group.

In formula (III), X³ represents an atom or a group selected arbitrarilyfrom a hydrogen atom, a halogen atom, an oxygen atom, a hydrocarbongroup, an oxygen-containing group, a nitrogen-containing group, aboron-containing group, a sulfur-containing group, aphosphorus-containing group, a halogen-containing group, a heterocycliccompound residue, a silicon-containing group, an aluminum-containinggroup, a germanium-containing group and a tin-containing group.

When n in formula (I) is 2 or more, a plurality of groups represented byX¹ may be the same or different; when n in formula (II) is 2 or more, aplurality of groups represented by X² may be the same or different; andwhen n in formula (III) is 2 or more, a plurality of groups representedby X³ may be the same or different.

When n in formula (I) is 2 or more, a plurality of groups represented byX¹ may be bound to one another to form a ring; when n in formula (II) is2 or more, a plurality of groups represented by X² may be bound to oneanother to form a ring; and when n in formula (III) is 2 or more, aplurality of groups represented by X³ may be bound to one another toform a ring.

The halogen atom represented by X¹ in formula (I), X² in formula (II)and X³ in formula (III) includes fluorine, chlorine, bromine and iodine.

The hydrocarbon group represented by X¹ in formula (I) X² in formula(II) and in formula (III) includes the same groups as illustrated for R¹to R⁷ in formula (I). Examples thereof include an alkyl group such asmethyl, ethyl, propyl, butyl, hexyl, octyl, nonyl, dodecyl, eicosyletc.; a C₃₋₃₀ cycloalkyl group such as cyclopentyl, cyclohexyl,norbornyl, adamantyl etc.; an alkenyl group such as vinyl, propenyl,cyclohexenyl etc.; an arylalkyl group such as benzyl, phenylethyl,phenylpropyl etc.; and an aryl group such as phenyl, tolyl,dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenylyl,naphthyl, methylnaphthyl, anthryl, phenanthryl etc. The hydrocarbongroup includes a halogenated hydrocarbon, specifically a C₁₋₂₀hydrocarbon group wherein at least one hydrogen atom is replaced by ahalogen. Among these, the C₁₋₂₀ hydrocarbon group is preferable.

The oxygen-containing group represented by X¹ in formula (I), X² informula (II) and X in formula (III) includes the same groups asillustrated for R¹ to R²¹ described above, and examples thereof includea hydroxy group; an alkoxy group such as methoxy, ethoxy, propoxy,butoxy etc.; an aryloxy group such as phenoxy, methylphenoxy,dimethylphenoxy, naphthoxy etc.; an arylalkoxy group such asphenylmethoxy, phenylethoxy etc.; an acetoxy group; a carbonyl groupetc.

The nitrogen-containing group represented by X¹ in formula (I), X² informula (II) and X³ in formula (III) includes the same groups asillustrated for R¹ to R²¹ described above, and examples thereof includean amino group; an alkylamino group such as methylamino, dimethylamino,diethylamino, dipropylamino, dibutylamino, dicyclohexylamino etc; and anarylamino group or an alkylarylamino group such as phenylamino,diphenylamino, ditolylamino, dinaphthylamino, methylphenylamino etc.

Specifically, the boron-containing group represented by X¹ in formula(I), X² in formula (II) and X³ in formula (III) includes BR₄ wherein Ris hydrogen, an alkyl group, an optionally substituted aryl group, ahalogen atom etc.

The sulfur-containing group represented by X¹ in formula (I), X² informula (II) and X³ in formula (III) includes the same groups asillustrated for R¹ to R²¹ described above, and examples thereof includea sulfonate group such as methyl sulfonate, trifluoromethane sulfonate,phenyl sulfonate, benzyl sulfonate, p-toluene sulfonate,trimethylbenzene sulfonate, triisobutylbenzene sulfonate,p-chlorobenzene sulfonate, pentafluorobenzene sulfonate etc.; asulfinate group such as methyl sulfinate, phenyl sulfinate, benzylsulfinate, p-toluene sulfinate, trimethylbenzene sulfinate,pentafluorobenzene sulfinate etc.; an alkylthio group; and an arylthiogroup.

The phosphorus-containing group represented by X¹ in formula (I), X² informula (II) and X³ in formula (III) includes, for example, atrialkylphosphine group such as trimethylphosphine, tributylphosphine,tricyclohexylphosphine etc.; a triarylphosphine group such astriphenylphosphine, tritolylphosphine etc.; a phosphite group (phosphidegroup) such as methylphosphite, ethylphosphite, phenylphosphite etc.; aphosphonic acid group; and a phosphinic acid group.

Specifically, the halogen-containing group represented by X¹ in formula(I), X² in formula (II) and X³ in formula (III) includes afluorine-containing group such as PF₆, BF₄ etc., a chlorine-containinggroup such as ClO₄, SbCl₆ etc., and an iodine-containing group such asIO₄ etc.

The heterocyclic compound residue represented by X¹ in formula (I), X²in formula (II) and X³ in formula (III) includes the same groups asillustrated for R¹ to R²¹ described above.

Specifically, the silicon-containing group represented by X in formula(I), X² in formula (II) and X³ in formula (III) includes the same groupsas illustrated for R¹ to R²¹ described above, and examples thereofinclude a hydrocarbon-substituted silyl group such as phenylsilyl,diphenylsilyl, trimethylsilyl, triethylsilyl, tripropylsilyl,tricyclohexylsilyl, triphenylsilyl, methyldiphenylsilyl, tritolylsilyl,trinaphthylsilyl etc.; a hydrocarbon-substituted silylether group suchas trimethylsilylether; a silicon-substituted alkyl group such astrimethylsilylmethyl etc.; and a silicon-substituted aryl group such astrimethylsilylphenyl etc.

Specifically, the aluminum-containing group represented by X¹ in formula(I), X² in formula (II) and X³ in formula (III) includes AlR₄ wherein Rrepresents hydrogen, an alkyl group, an optionally substituted arylgroup, a halogen atom etc.

Specifically, the germanium-containing group represented by X¹ informula (I), X² in formula (II) and X³ in formula (III) includes thesame groups as illustrated for R¹ to R²¹ described above.

Specifically, the tin-containing group represented by X¹ in formula (I),X² in formula (II) and X³ in formula (III) includes the same groups asillustrated for R¹ to R²¹ described above.

Specific examples of the transition metal compound represented by thegeneral formula (I), (II) or (III) above are described below.

In the following examples, M is a transition metal atom, and preferableexamples are Sc(III), Ti(III), Ti (IV), Zr(III) Zr(IV), Hf(IV), V(III),V(IV), V(V), Nb(V), Ta(V), Fe(II), Fe(III), Co(II), Co(III), Rh(II),Rh(III), Rh(IV), Cr(III), Ni(II) and Pd(II). Among these metal atoms,Ti(IV), Zr(IV), Hf(IV), V(III), V(IV), V(V), Nb(V) and Ta(V) arepreferable, and particularly Ti(IV), Zr(IV) and Hf(IV) are preferable.

In the following examples, X represents for example a halogen such asCl, Br etc., an oxygen atom or an alkyl group such as methyl etc. Whenthere are a plurality of Xs, the Xs may be the same or different.

n is determined by the valence of the metal M. For example, when twomonoanion species bind to the metal, n is 0 for divalent metal, n is 1for trivalent metal, n is 2 for tetravalent metal, and n is 3 forpentavalent metal; for example, n is 1 for a metal V(III), n is 2 forTi(IV), Zr(IV) or V(IV) and n is 3 for V(V) for example, when one kindof monoanion species binds to the metal and simultaneously one oxygenatom bind via a double bond to the metal, n is 0 for trivalent metal, nis 1 for tetravalent metal, and n is 2 for pentavalent metal; forexample, n is 0 for a metal V(III), n is 1 for Ti(IV), Zr(IV) or V(IV),and n is 2 for V(V); for example, when two monoanion species bind to themetal and simultaneously one oxygen atom binds via a double bond to themetal, n is 0 for tetravalent metal and n is 1 for pentavalent metal;for example, n is 0 for a metal Ti (IV), Zr (IV) or V(IV) and n is 1 forV(V); for example, when one kind of monoanion species binds to the metaland simultaneously one atom binds via a single bond to the metal, n is 0for divalent metal, n is 1 for trivalent metal, n is 2 for tetravalentmetal and n is 3 for pentavalent metal; for example, n is 1 for a metalV(III) n is 2 for Ti (IV), Zr(IV) or V(IV), and n is 3 for V(V).

Specific examples of the transition metal compound represented by thegeneral formula (I), (II) or (III) are shown below.

In the above-illustrated compounds, tBu indicates a t-butyl group, OMeindicates a methoxy group, Ph indicates a phenyl group, Me indicates amethyl group, and Adm indicates an adamanthyl group.

The transition metal compounds in the present invention can also beexemplified by those derivatives of the above compounds whereinzirconium was replaced by a metal selected from the groups 4 and 5 inthe periodic table, such as titanium, hafnium, vanadium etc.

Compound (a-2)

As the component (A) in the present invention, compound (a-2)represented by the following general formula (IVa) can be used.

In formula (IVa), M is a transition metal atom selected from the groups3 to 7 in the periodic table, preferably a transition metal atomselected from the groups 4 and 5. Specifically, M is titanium,zirconium, hafnium, vanadium, niobium or tantalum, preferably titanium,zirconium or vanadium.

In formula (IVa), R¹ to R⁶ may be the same or different and eachrepresent a hydrogen atom, a halogen atom, a hydrocarbon group, anoxygen-containing group, a nitrogen-containing group, a boron-containinggroup, a sulfur-containing group, a phosphorus-containing group, aheterocyclic compound residue, a silicon-containing group, agermanium-containing group or a tin-containing group, and two or more ofthese groups may be bound to each other to form a ring such as anaromatic ring, an aliphatic ring, or a hydrocarbon ring containing aheteroatom such as a nitrogen atom, a sulfur atom and an oxygen atom.Each of R⁵ and R⁶ is preferably a hydrocarbon group, more preferably anaryl group substituted with an alkyl group.

The halogen atom and hydrocarbon group represented by R¹ to R⁶ informula (IVa) include the same halogen atoms and hydrocarbon groups asillustrated for R¹ to R⁷ in the formula (I) above.

The hydrocarbon group represented by R¹ to R⁶ in formula (IVa) may besubstituted with an oxygen-containing group, a nitrogen-containinggroup, a boron-containing group, a sulfur-containing group, aphosphorus-containing group, a silicon-containing group, agermanium-containing group, a tin-containing group etc., wherein anatomic group characterizing the substituent group such as theoxygen-containing group is desirably not directly bound to N in formula(IVa).

The hydrocarbon group is particularly a C₁₋₃₀, preferably C₁₋₂₀, linearor branched alkyl group such as methyl, ethyl, n-propyl, isopropyl,n-butyl, isobutyl, sec-butyl, t-butyl, neopentyl, n-hexyl etc.; a C₆₋₃₀,preferably C₆₋₂₀, aryl group such as phenyl, naphthyl, biphenylyl,terphenylyl, phenanthryl, anthryl etc.; and a substituted aryl groupsubstituted with 1 to 5 substituent atoms or groups such as a halogenatom, a C₁₋₃₀, preferably C₁₋₂₀, alkyl group or alkoxy group, a C₆₋₃₀,preferably C₆₋₂₀, aryl group or aryloxy group.

In formula (IVa), two or more groups of R¹ to R⁶, preferably adjacentgroups, may be bound to each other to form an aromatic ring, analiphatic ring, or a hydrocarbon ring containing a nitrogen atom, asulfur atom, an oxygen atom etc., and these rings may further have asubstituent group, and particularly R³ and R⁴ are preferably bound toeach other to form an aromatic ring.

The oxygen-containing group, nitrogen-containing group, boron-containinggroup, sulfur-containing group, phosphorus-containing group,heterocyclic compound residue, silicon-containing group,germanium-containing group and tin-containing group represented by R¹ toR⁶ in formula (IVa) include the same groups as illustrated for R¹ to R⁷in the formula (I) above.

More specific groups of R¹ to R⁶ in formula (IVa) include the morespecific groups illustrated as R¹ to R⁷ in the formula (I) above.

In formula (IVa), n is a number satisfying the valence of M, and isspecifically an integer of 1 to 5, preferably 1 to 4, more preferably 1to 3.

In formula (IVa), X represents a hydrogen atom, a halogen atom, ahydrocarbon group, an oxygen-containing group, a sulfur-containinggroup, a nitrogen-containing group, a boron-containing group, analuminum-containing group, a phosphorus-containing group, ahalogen-containing group, a heterocyclic compound residue, asilicon-containing group, a germanium-containing group or atin-containing group.

The halogen atom, hydrocarbon group, oxygen-containing group,sulfur-containing group, nitrogen-containing group, boron-containinggroup, aluminum-containing group, phosphorus-containing group,halogen-containing group, heterocyclic compound residue,silicon-containing group, germanium-containing group and tin-containinggroup represented by X in formula (IVa) include the same atoms or groupsas illustrated for X¹ in the formula (I) above.

The hydrocarbon group is preferably a C₁₋₂₀ group.

When n is 2 or more, a plurality of groups represented by Xs may be thesame or different, and a plurality of groups represented by Xs may bebound to one another to form a ring.

Compound (a-2) represented by the general formula (IVa) above ispreferably a compound represented by the following general formula(Iva′):

In formula (Iva′), M is a transition metal atom selected from the groups4 and 5 in the periodic table, and specifically M is titanium,zirconium, vanadium, niobium or tantalum.

In formula (Iva′), R⁷ to R¹³ may be the same or different and eachrepresent a hydrogen atom, a halogen atom, a hydrocarbon group, anoxygen-containing group, a nitrogen-containing group, a boron-containinggroup, a sulfur-containing group, a phosphorus-containing group, aheterocyclic compound residue, a silicon-containing group, agermanium-containing group or a tin-containing group, and two or more ofthese groups may be bound to each other to form a ring. Each of R¹² andR¹³ is preferably a hydrocarbon group, more preferably an aryl groupsubstituted with an o-alkyl group.

The halogen atom and hydrocarbon group represented by R⁷ to R¹³ informula (Iva′) include the same atoms and groups as illustrated for R¹to R⁷ in the general formula (I) above.

The hydrocarbon group may be substituted with an oxygen-containinggroup, a nitrogen-containing group, a boron-containing group, asulfur-containing group, a phosphorus-containing group, asilicon-containing group, a germanium-containing group, a tin-containinggroup etc., wherein an atomic group characterizing the substituent groupsuch as the oxygen-containing group is desirably not directly bound to Nin formula (Iva′).

The oxygen-containing group, nitrogen-containing group, boron-containinggroup, sulfur-containing group, phosphorus-containing group,heterocyclic compound residue, silicon-containing group,germanium-containing group and tin-containing group represented by R⁷ toR¹³ in formula (Iva′) include the same groups as illustrated for R¹ toR⁷ in the general formula (I) above.

More specific groups of R⁷ to R¹³ in formula (Iva′) include the morespecific groups illustrated above as those of R¹ to R⁷ in the formula(I) above.

In formula (Iva′), n is a number satisfying the valence of M, and isspecifically an integer of 1 to 5, preferably 1 to 4, more preferably 1to 3.

In formula (Iva′), X represents a hydrogen atom, a halogen atom, ahydrocarbon group, an oxygen-containing group, a sulfur-containinggroup, a nitrogen-containing group, a boron-containing group, aphosphorus-containing group, a halogen-containing group, a heterocycliccompound residue, an aluminum-containing group, a silicon-containinggroup, a germanium-containing group or a tin-containing group.

The halogen atom, hydrocarbon group, oxygen-containing group,sulfur-containing group, nitrogen-containing group, boron-containinggroup, aluminum-containing group, phosphorus-containing group,halogen-containing group, heterocyclic compound residue,silicon-containing group, germanium-containing group and tin-containinggroup represented by X in formula (Iva′) include the same atoms orgroups as illustrated for X¹ in the formula (I) above.

When n is 2 or more, a plurality of groups represented by Xs may be thesame or different, and a plurality of groups represented by Xs may bebound to one another to form a ring.

Specific examples of the compounds represented by the general formula(IVa) above are shown below.

In the above-illustrated compounds, iPr indicates an isopropyl group,tBu indicates a t-butyl group, and Ph indicates a phenyl group.

Compound (a-3)

As the component (A) in the present invention, compound (a-3)represented by the following general formula (IVb) can be used.

In formula (IVb), M is a transition metal atom selected from the groups8 to 11 in the periodic table, preferably a transition metal atomselected form the group 8 and 9. Specifically, M is iron, ruthenium,osmium, cobalt, rhodium, iridium, nickel, palladium, copper etc.,preferably iron, ruthenium, cobalt, rhodium etc., more preferably ironor cobalt.

In formula (IVb), R¹ to R⁶ may be the same or different and eachrepresent a hydrogen atom, a halogen atom, a hydrocarbon group, anoxygen-containing group, a nitrogen-containing group, a boron-containinggroup, a sulfur-containing group, a phosphorus-containing group, aheterocyclic compound residue, a silicon-containing group, agermanium-containing group or a tin-containing group, and two or more ofthese groups may be bound to each other to form a ring such as anaromatic ring, an aliphatic ring, or a hydrocarbon ring containing aheteroatom such as a nitrogen atom, a sulfur atom and an oxygen atom.Each of R⁵ and R⁶ is preferably a hydrocarbon group, more preferably anaryl group substituted with an alkyl group.

The halogen atom and hydrocarbon group represented by R¹ to R⁶ informula (IVb) include the same halogen atoms and hydrocarbon groups asillustrated for R¹ to R⁷ in the formula (I) above.

The hydrocarbon group represented by R¹ to R⁶ in formula (IVb) may besubstituted with an oxygen-containing group, a nitrogen-containinggroup, a boron-containing group, a sulfur-containing group, aphosphorus-containing group, a silicon-containing group, agermanium-containing group, a tin-containing group etc., wherein anatomic group characterizing the substituent group such as theoxygen-containing group is desirably not directly bound to N in formula(IVb).

The hydrocarbon group is particularly a C₁₋₃₀, preferably C₁₋₂₀, linearor branched alkyl group such as methyl, ethyl, n-propyl, isopropyl,n-butyl, isobutyl, sec-butyl, t-butyl, neopentyl, n-hexyl etc.; a C₆₋₃₀,preferably C₆₋₂₀, aryl group such as phenyl, naphthyl, biphenylyl,terphenylyl, phenanthryl, anthryl etc.; and a substituted aryl groupsubstituted with 1 to 5 substituent atoms or groups such as a halogenatom, a C₁₋₃₀, preferably C₁₋₂₀, alkyl group or alkoxy group, a C₆₋₃₀,preferably C₆₋₂₀, aryl group or aryloxy group.

In formula (IVb), two or more groups of R¹ to R⁶, preferably adjacentgroups, may be bound to each other to form an aromatic ring, analiphatic ring, or a hydrocarbon ring containing a nitrogen atom, asulfur atom, an oxygen atom etc., and these rings may further have asubstituent group, and particularly R³ and R⁴ are preferably bound toeach other to form an aromatic ring.

The oxygen-containing group, nitrogen-containing group, boron-containinggroup, sulfur-containing group, phosphorus-containing group,heterocyclic compound residue, silicon-containing group,germanium-containing group and tin-containing group represented by R¹ toR⁶ in formula (IVb) include the same groups as illustrated for R¹ to R⁷in the formula (I) above.

More specific groups of R¹ to R⁶ in formula (IVb) include the morespecific groups illustrated above as those of R¹ to R⁷ in the formula(I) above.

In formula (IVb), n is a number satisfying the valence of M, and isspecifically an integer of 1 to 5, preferably 1 to 4, more preferably 1to 3.

In formula (IVb), X represents a hydrogen atom, a halogen atom, ahydrocarbon group, an oxygen-containing group, a sulfur-containinggroup, a nitrogen-containing group, a boron-containing group, analuminum-containing group, a phosphorus-containing group, ahalogen-containing group, a heterocyclic compound residue, asilicon-containing group, a germanium-containing group or atin-containing group.

The halogen atom, hydrocarbon group, oxygen-containing group,sulfur-containing group, nitrogen-containing group, boron-containinggroup, aluminum-containing group, phosphorus-containing group,halogen-containing group, heterocyclic compound residue,silicon-containing group, germanium-containing group and tin-containinggroup represented by X in formula (IVb) include the same atoms or groupsas illustrated for X¹ in the formula (I) above.

The hydrocarbon group is preferably a C₁₋₂₀ group.

When n is 2 or more, a plurality of groups represented by Xs may be thesame or different, and a plurality of groups represented by Xs may bebound to one another to form a ring.

Compound (a-3) represented by the general formula (IVb) above ispreferably a compound represented by the following general formula(Ivb′)

In formula (Ivb′), M is a transition metal atom selected from the groups8 and 9 in the periodic table, and specifically M is iron or cobalt.

In formula (Ivb′), R⁷ to R¹³ may be the same or different and eachrepresent a hydrogen atom, a halogen atom, a hydrocarbon group, anoxygen-containing group, a nitrogen-containing group, a boron-containinggroup, a sulfur-containing group, a phosphorus-containing group, aheterocyclic compound residue, a silicon-containing group, agermanium-containing group or a tin-containing group, and two or more ofthese groups may be bound to each other to form a ring. Each of R² andR³ is preferably a hydrocarbon group, more preferably an aryl groupsubstituted with an o-alkyl group.

The halogen atom and hydrocarbon group represented by R⁷ to R¹³ informula (Ivb′) include the same atoms and groups as illustrated for R¹to R⁷ in the general formula (I) above.

The hydrocarbon group may be substituted with an oxygen-containinggroup, a nitrogen-containing group, a boron-containing group, asulfur-containing group, a phosphorus-containing group, asilicon-containing group, a germanium-containing group, a tin-containinggroup etc., wherein an atomic group characterizing the substituent groupsuch as the oxygen-containing group is desirably not directly bound to Nin formula (Ivb′).

The oxygen-containing group, nitrogen-containing group, boron-containinggroup, sulfur-containing group, phosphorus-containing group,heterocyclic compound residue, silicon-containing group,germanium-containing group and tin-containing group represented by R⁷ toR¹³ in formula (Ivb′) include the same groups as illustrated for R¹ toR⁷ in the general formula (I) above.

More specific groups of R⁷ to R¹³ in formula (IVb′) include the morespecific groups illustrated above as those of R¹ to R⁷ in the formula(I) above.

In formula (Ivb′), n is a number satisfying the valence of M, and isspecifically an integer of 1 to 5, preferably 1 to 4, more preferably 1to 3.

In formula (Ivb′), X represents a hydrogen atom, a halogen atom, ahydrocarbon group, an oxygen-containing group, a sulfur-containinggroup, a nitrogen-containing group, a boron-containing group, aphosphorus-containing group, a halogen-containing group, a heterocycliccompound residue, an aluminum-containing group, a silicon-containinggroup, a germanium-containing group or a tin-containing group.

The halogen atom, hydrocarbon group, oxygen-containing group,sulfur-containing group, nitrogen-containing group, boron-containinggroup, aluminum-containing group, phosphorus-containing group,halogen-containing group, heterocyclic compound residue,silicon-containing group, germanium-containing group and tin-containinggroup represented by X in formula (Ivb′) include the same atoms orgroups as illustrated for X¹ in the formula (I) above.

When n is 2 or more, a plurality of groups represented by Xs may be thesame or different, and a plurality of groups represented by Xs may bebound to one another to form a ring.

Specific examples of the compounds represented by the general formula(IVb) above are shown below.

In the above-illustrated compounds, iPr indicates an isopropyl group,tBu indicates a t-butyl group, and Ph indicates a phenyl group.

In the present invention, transition metal compounds wherein in thecompounds described above, iron was replaced by a non-iron metal such asrhodium and cobalt selected from the groups 8 to 11 in the periodictable can also be mentioned.

Compound (a-4)

As the component (A) in the present invention, compound (a-4)represented by the following general formula (IVc) can be used.

In formula (IVc), M is a transition metal atom selected from the groups3 to 11 in the periodic table, preferably a transition metal atomselected from the groups 4 and 5 and the groups 8 and 9. Specifically, Mis titanium, zirconium, hafnium, vanadium, niobium, tantalum, iron,rhenium, osmium, cobalt, rhodium, iridium, nickel, palladium, copperetc., preferably titanium, zirconium, vanadium, niobium, tantalum, iron,rhenium, cobalt, rhodium etc., more preferably titanium, zirconium,vanadium, iron or cobalt.

In formula (IVc), m is an integer of 1 to 6, preferably an integer of 1to 4, more preferably an integer of 1 to 3, still more preferably aninteger of 1 to 2.

In formula (IVc), R¹ to R⁶ may be the same or different and eachrepresent a hydrogen atom, a halogen atom, a hydrocarbon group, anoxygen-containing group, a nitrogen-containing group, a boron-containinggroup, a sulfur-containing group, a phosphorus-containing group, aheterocyclic compound residue, a silicon-containing group, agermanium-containing group or a tin-containing group, and two or more ofthese groups may be bound to each other to form a ring such as anaromatic ring, an aliphatic ring, or a hydrocarbon ring containing aheteroatom such as a nitrogen atom, a sulfur atom and an oxygen atom.Each of R⁵ and R⁶ is preferably a hydrocarbon group, more preferably anaryl group substituted with an alkyl group.

The halogen atom and hydrocarbon group represented by R¹ to R⁶ informula (IVc) include the same halogen atoms and hydrocarbon groups asillustrated for R¹ to R⁷ in the formula (I) above.

The hydrocarbon group represented by R¹ to R⁶ in formula (IVc) may besubstituted with an oxygen-containing group, a nitrogen-containinggroup, a boron-containing group, a sulfur-containing group, aphosphorus-containing group, a silicon-containing group, agermanium-containing group, a tin-containing group etc., wherein anatomic group characterizing the substituent group such as theoxygen-containing group is desirably not directly bound to N in formula(IVc).

The hydrocarbon group is particularly a C₁₋₃₀, preferably C₁₋₂₀, linearor branched alkyl group such as methyl, ethyl, n-propyl, isopropyl,n-butyl, isobutyl, sec-butyl, t-butyl, neopentyl, n-hexyl etc.; a C₆₋₃₀,preferably C₆₋₂₀, aryl group such as phenyl, naphthyl, biphenylyl,terphenylyl, phenanthryl, anthryl etc.; and a substituted aryl groupsubstituted with 1 to 5 substituent atoms or groups such as a halogenatom, a C₁₋₃₀, preferably C₁₋₂₀, alkyl group or alkoxy group, a C₆₋₃₀,preferably C₆₋₂₀, aryl group or aryloxy group.

In formula (IVc), two or more groups of R¹ to R⁶, preferably adjacentgroups, may be bound to each other to form an aromatic ring, analiphatic ring, or a hydrocarbon ring containing a nitrogen atom, asulfur atom, an oxygen atom etc., and these rings may further have asubstituent group, and particularly R³ and R⁴ are preferably bound toeach other to form an aromatic ring.

The oxygen-containing group, nitrogen-containing group, boron-containinggroup, sulfur-containing group, phosphorus-containing group,heterocyclic compound residue, silicon-containing group,germanium-containing group and tin-containing group represented by R¹ toR⁶ in formula (IVc) include the same groups as illustrated for R¹ to R⁷in the formula (I) above.

More specific groups of R¹ to R⁶ in formula (IVc) include the morespecific groups illustrated above as those of R¹ to R⁷ in the formula(I) above.

In formula (IVc), n is a number satisfying the valence of M, and isspecifically an integer of 1 to 5, preferably 1 to 4, more preferably 1to 3.

When n is 1, X is an oxygen atom, and when n is 2 or more, at least oneof Xs is an oxygen atom, and other Xs represent a hydrogen atom, ahalogen atom, an oxygen atom, a hydrocarbon group, an oxygen-containinggroup, a sulfur-containing group, a nitrogen-containing group, aboron-containing group, an aluminum-containing group, aphosphorus-containing group, a halogen-containing group, a heterocycliccompound residue, a silicon-containing group, a germanium-containinggroup or a tin-containing group.

The halogen atom, hydrocarbon group, oxygen-containing group,sulfur-containing group, nitrogen-containing group, boron-containinggroup, aluminum-containing group, phosphorus-containing group,halogen-containing group, heterocyclic compound residue,silicon-containing group, germanium-containing group and tin-containinggroup represented by X in formula (IVc) include the same atoms or groupsas illustrated for X¹ in the formula (I) above.

The hydrocarbon group is preferably a C₁₋₂₀ group.

When n is 2 or more, a plurality of groups represented by Xs may be thesame or different, and a plurality of groups represented by Xs may bebound to one another to form a ring.

Compound (a-4) represented by the general formula (IVc) above ispreferably a compound represented by the following general formula(Ivc′):

In formula (Ivc′), M is a transition metal atom selected from the groups4 and 5 and the groups 8 and 9 in the periodic table, and specifically Mis titanium, zirconium, vanadium, niobium, tantalum, iron or cobalt.

In formula (Ivc′), m is an integer of 1 to 6, preferably an integer of 1to 4, more preferably an integer of 1 to 3, still more preferably aninteger of 1 to 2.

In formula (Ivc′), R⁷ to R¹³ may be the same or different and eachrepresent a hydrogen atom, a halogen atom, a hydrocarbon group, anoxygen-containing group, a nitrogen-containing group, a boron-containinggroup, a sulfur-containing group, a phosphorus-containing group, aheterocyclic compound residue, a silicon-containing group, agermanium-containing group or a tin-containing group, and two or more ofthese groups may be bound to each other to form a ring. Each of R¹² andR¹³ is preferably a hydrocarbon group, more preferably an aryl groupsubstituted with an o-alkyl group.

The halogen atom and hydrocarbon group represented by R⁷ to R¹³ informula (Ivc′) include the same atoms and groups as illustrated for R¹to R⁷ in the general formula (I) above.

The hydrocarbon group may be substituted with an oxygen-containinggroup, a nitrogen-containing group, a boron-containing group, asulfur-containing group, a phosphorus-containing group, asilicon-containing group, a germanium-containing group, a tin-containinggroup etc., wherein an atomic group characterizing the substituent groupsuch as the oxygen-containing group is desirably not directly bound to Nin formula (Ivc′).

The oxygen-containing group, nitrogen-containing group, boron-containinggroup, sulfur-containing group, phosphorus-containing group,heterocyclic compound residue, silicon-containing group,germanium-containing group and tin-containing group represented by R⁷ toR¹³ in formula (Ivc′) include the same groups as illustrated for R¹ toR⁷ in the general formula (I) above.

More specific groups of R⁷ to R¹³ in formula (Ivc′) include the morespecific groups illustrated above as those of R¹ to R⁷ in the formula(I) above.

In formula (Ivc′), n is a number satisfying the valence of M, and isspecifically an integer of 1 to 5, preferably 1 to 4, more preferably 1to 3.

When n is 1, X is an oxygen atom, and when n is 2 or more, at least oneof Xs is an oxygen atom, and other Xs represent a hydrogen atom, ahalogen atom, an oxygen atom, a hydrocarbon group, an oxygen-containinggroup, a sulfur-containing group, a nitrogen-containing group, aboron-containing group, a phosphorus-containing group, ahalogen-containing group, a heterocyclic compound residue, analuminum-containing group, a silicon-containing group, agermanium-containing group or a tin-containing group.

The halogen atom, hydrocarbon group, oxygen-containing group,sulfur-containing group, nitrogen-containing group, boron-containinggroup, aluminum-containing group, phosphorus-containing group,halogen-containing group, heterocyclic compound residue,silicon-containing group, germanium-containing group and tin-containinggroup represented by X in formula (Ivc′) include the same atoms orgroups as illustrated for X¹ in the formula (I) above.

When n is 2 or more, a plurality of groups represented by Xs may be thesame or different, and a plurality of groups represented by Xs may bebound to one another to form a ring.

Compound (a-5)

As the component (A) in the present invention, compound (a-5)represented by the following general formula (V) can be used.

In formula (V), M is a transition metal atom selected from the groups 3to 6 in the periodic table, preferably the group 4 atom, andspecifically M is titanium, zirconium or hafnium.

In formula (V), R and R″ may be the same or different and each representa hydrogen atom, a C₁₋₅₀ hydrocarbon group, a C₁₋₅₀ halogenatedhydrocarbon group, an organic silyl group, or a substituent group havingat least one atom selected from nitrogen, oxygen, phosphorus, sulfur andsilicon, preferably a hydrocarbon group.

The C₁₋₅₀ hydrocarbon group and C₁₋₅₀ halogenated hydrocarbon grouprepresented by R and R′ in formula (V) include, for example, thehydrocarbon group and halogenated hydrocarbon group illustrated as R¹ toR⁷ in the general formula (I) above; the organic silyl group representedby R and R′ includes, for example, the silicon-containing groupillustrated as R¹ to R⁷ in the general formula (I) above; and thesubstituent group having at least one atom selected from nitrogen,oxygen, phosphorus, sulfur and silicon represented by R and R′ includes,for example, the nitrogen-, oxygen-, phosphorus-, sulfur- orsilicon-containing residue out of the nitrogen-containing group,oxygen-containing group, sulfur-containing group and heterocycliccompound residue illustrated as R¹ to R⁷ in the general formula (I)above.

In formula (V), n is a number satisfying the valence of M, and isspecifically an integer of 1 to 5, preferably 1 to 4, more preferably 1to 3.

In formula (V), Xs may be the same or different and each represent ahydrogen atom, a halogen atom, an oxygen atom, a C₁₋₂₀ hydrocarbongroup, a C₁₋₂₀ halogenated hydrocarbon group, an oxygen-containinggroup, a sulfur-containing group, a silicon-containing group or anitrogen-containing group, and Xs may be bound to each other to form aring.

The halogen atom, C₁₋₂₀ hydrocarbon group, C₁₋₂₀ halogenated hydrocarbongroup, oxygen-containing group, sulfur-containing group,silicon-containing group and nitrogen-containing group represented by Xin formula (V) include, for example, the halogen atom, hydrocarbongroup, halogenated hydrocarbon group, oxygen-containing group,sulfur-containing group, silicon-containing group andnitrogen-containing group illustrated as R¹ to R⁷ in the general formula(I) above.

Specific examples of the compounds represented by the general formula(V) above are shown below.

In the above-illustrated compounds, ^(n)Bu indicates an n-butyl group,Me indicates a methyl group, ^(i)Pr indicates an isopropyl group, and Phindicates a phenyl group.

Compound (a-6)

As the component (A) in the present invention, compound (a-6)represented by the following general formula (VI) can be used.

In formula (VI), M is a transition metal atom selected from the groups 4and 5 in the periodic table, and specifically M is titanium, zirconium,hafnium, vanadium, niobium or tantalum.

In formula (VI), R¹ to R¹⁰ may be the same or different and eachrepresent a hydrogen atom, a C₁₋₅₀ hydrocarbon group, a C₁₋₅₀halogenated hydrocarbon group, an organic silyl group, or a hydrocarbongroup substituted with a substituent group containing at least one atomselected from nitrogen, oxygen, phosphorus, sulfur and silicon, andpreferably represent hydrogen or a hydrocarbon group. The groupsrepresented by R¹ to R¹⁰ may be bound to each other to form a ring.

The C₁₋₅₀ hydrocarbon group and C₁₋₅₀ halogenated hydrocarbon grouprepresented by R¹ to R¹⁰ in formula (VI) include, for example, thehydrocarbon group and halogenated hydrocarbon group illustrated as R¹ toR⁷ in the general formula (I) above; the organic silyl group representedby R¹ to R¹⁰ includes, for example, the silicon-containing groupillustrated as R¹ to R⁷ in the general formula (I) above; and thehydrocarbon group substituted with a substituent group containing atleast one atom selected from nitrogen, oxygen, phosphorus, sulfur andsilicon, represented by R¹ to R¹⁰, includes, for example, the nitrogen-,oxygen-, phosphorus-, sulfur- or silicon-containing residue out of thenitrogen-containing group, oxygen-containing group, sulfur-containinggroup and heterocyclic compound residue illustrated as R¹ to R⁷ in thegeneral formula (I) above.

In formula (VI), n is a number satisfying the valence of M, and isspecifically an integer of 1 to 5, preferably 1 to 4, more preferably 1to 3.

In formula (VI), X represent a hydrogen atom, a halogen atom, an oxygenatom, a C₁₋₂₀ hydrocarbon group, a C₁₋₂₀ halogenated hydrocarbon group,an oxygen-containing group, a sulfur-containing group, asilicon-containing group or a nitrogen-containing group, preferably ahalogen atom. When n is 2 or more, a plurality of groups represented byXs may be the same or different.

The halogen atom, C₁₋₂₀ hydrocarbon group, C₁₋₂₀ halogenated hydrocarbongroup, oxygen-containing group, sulfur-containing group,silicon-containing group and nitrogen-containing group represented by Xin formula (VI) include, for example, the halogen atom, hydrocarbongroup, halogenated hydrocarbon group, oxygen-containing group,sulfur-containing group, silicon-containing group andnitrogen-containing group illustrated as R¹ to R⁷ in the general formula(I) above.

In formula (VI), Y represents an atom selected from the groups 15 and 16in the periodic table. Specifically, Y represents a nitrogen,phosphorus, arsenic, antimony, oxygen or sulfur atom, preferably anitrogen or oxygen atom.

Specific examples of the compounds represented by the general formula(VI) above are shown below.

In the above-illustrated compounds, Ph indicates a phenyl group.

Compound (a-7)

As the component (A) in the present invention, compound (a-7)represented by the following general formula (VII) or (VIII) can beused.

In formula (VII) or (VIII), M is a transition metal atom selected fromthe groups 4 and 5 in the periodic table, and specifically M istitanium, zirconium, hafnium, vanadium, niobium or tantalum.

R¹ to R⁶ in formula (VII) and R⁷ to R¹⁰ in formula (VIII) may be thesame or different and each represent hydrogen, a C₁₋₅₀ hydrocarbongroup, a C1 to 50 halogenated hydrocarbon group, an organic silyl group,or a hydrocarbon group substituted with a substituent group containingat least one atom selected from nitrogen, oxygen, phosphorus, sulfur andsilicon, and preferably represent hydrogen or a hydrocarbon group. Atleast two groups out of the groups represented by R¹ to R⁶ in formula(VII) and R⁷ to R¹⁰ in formula (VIII) may be bound to each other to forma ring.

The C₁₋₅₀ hydrocarbon group and C₁₋₅₀ halogenated hydrocarbon grouprepresented by R¹ to R⁶ in formula (VII) and R⁷ to R¹⁰ in formula (VIII)include, for example, the hydrocarbon group and halogenated hydrocarbongroup illustrated as R¹ to R⁷ in the general formula (I) above; theorganic silyl group represented by R¹ to R⁶ in formula (VII) and R⁷ toR¹⁰ in formula (VIII) includes, for example, the silicon-containinggroup illustrated as R¹ to R⁷ in the general formula (I) above; and thehydrocarbon group substituted with a substituent group containing atleast one atom selected from nitrogen, oxygen, phosphorus, sulfur andsilicon, represented by R¹ to R⁶ in formula (VII) and R⁷ to R¹⁰ informula (VIII), includes, for example, a hydrocarbon group substitutedwith the nitrogen-, oxygen-, phosphorus-, sulfur- or silicon-containingresidue out of the nitrogen-containing group, oxygen-containing group,sulfur-containing group and heterocyclic compound residue illustrated asR¹ to R⁷ in the general formula (I) above.

In formulae (VII) and (VIII), m is an integer of 1 to 6, preferably aninteger of 1 to 4, more preferably an integer of 1 to 2.

In formulae (VII) and (VIII), n is a number satisfying the valence of M,and is specifically an integer of 1 to 5, preferably 1 to 4, morepreferably 1 to 3.

In formulae (VII) and (VIII), X represent a hydrogen atom, a halogenatom, an oxygen atom, a C₁₋₂₀ hydrocarbon group, a C₁₋₂₀ halogenatedhydrocarbon group, an oxygen-containing group, a sulfur-containinggroup, a silicon-containing group or a nitrogen-containing group,preferably a halogen atom. When n is 2 or more, a plurality of groupsrepresented by Xs may be the same or different.

The halogen atom, C₁₋₂₀ hydrocarbon group, C₁₋₂₀ halogenated hydrocarbongroup, oxygen-containing group, sulfur-containing group,silicon-containing group and nitrogen-containing group represented by Xin formulae (VII) and (VIII) include, for example, the halogen atom,hydrocarbon group, halogenated hydrocarbon group, oxygen-containinggroup, sulfur-containing group, silicon-containing group andnitrogen-containing group illustrated as R¹ to R⁷ in the general formula(I) above.

In formulae (VII) and (VIII), Y represents the group 15 or 16 atom inthe periodic table, preferably the group 15 atom. Specifically, Yrepresents nitrogen, phosphorus, arsenic, antimony, oxygen or sulfur,preferably an oxygen atom.

Specific examples of the compounds represented by the general formula(VII) or (VIII) above are shown below.

In the above-illustrated compounds, Me indicates a methyl group.

Compound (a-8)

As the component (A) in the present invention, compound (a-8)represented by the following general formula (IX) can be used.

In formula (IX), M is a transition metal atom selected from the groups 3to 6 in the periodic table, preferably the group 4 transition metal.Specifically, M is scandium, yttrium, titanium, zirconium, hafnium,vanadium, niobium, tantalum, chromium, molybdenum or tungsten,preferably titanium, zirconium or hafnium.

In formula (IX), R and R′ may be the same or different and eachrepresent a hydrogen atom, a C₁₋₅₀ hydrocarbon group, a C₁₋₅₀halogenated hydrocarbon group, an organic silyl group, or a substituentgroup having at least one atom selected from nitrogen, oxygen,phosphorus, sulfur and silicon, preferably a hydrocarbon group.

The C₁₋₅₀ hydrocarbon group and C₁₋₅₀ halogenated hydrocarbon grouprepresented by R and R′ in formula (IX) include, for example, thehydrocarbon group and halogenated hydrocarbon group illustrated as R¹ toR⁷ in the general formula (I) above; the organic silyl group representedby R and R′ includes, for example, the silicon-containing groupsillustrated as R¹ to R⁷ in the general formula (I) above; and thesubstituent group having at least one atom selected from nitrogen,oxygen, phosphorus, sulfur and silicon represented by R and R′ includes,for example, the nitrogen-, oxygen-, phosphorus-, sulfur- orsilicon-containing residue out of the nitrogen-containing group,oxygen-containing group, sulfur-containing group and heterocycliccompound residue illustrated as R¹ to R⁷ in the general formula (I)above.

In formula (IX), m is an integer of 0 to 2, preferably 2.

In formula (IX), n is an integer of 1 to 5, preferably an integer of 1to 3.

In formula (IX), A represents an atom selected from the groups 13 to 16in the periodic table, preferably the group 14 atom in the periodictable. Specifically, A is boron, carbon, nitrogen, oxygen, silicon,phosphorus, sulfur, germanium or tin, preferably carbon or silicon. Whenn is 2 or more, a plurality of As may be the same or different.

In formula (IX), E is a substituent group having at least one kind ofatom selected from carbon, hydrogen, oxygen, halogen, nitrogen, sulfur,phosphorus, boron and silicon, and E is preferably hydrogen or a carbonatom. When a plurality of groups are represented by Es, a plurality ofgroups represented by Es may be the same or different, and two or moregroups represented by Es may be bound to each other to form a ring.

The substituent group having at least one kind of atom selected fromcarbon, hydrogen, oxygen, halogen, nitrogen, sulfur, phosphorus, boronand silicon, represented by E in formula (IX), includes the halogenatom, hydrocarbon group, oxygen-containing group, nitrogen-containinggroup, boron-containing group, sulfur-containing group,phosphorus-containing group, heterocyclic compound residue andsilicon-containing group illustrated as R¹ to R⁷ in the general formula(I) above.

In formula (IX), p is an integer of 0 to 4, preferably 2.

In formula (IX), X represents a hydrogen atom, a halogen atom, an oxygenatom, a C₁₋₂₀ hydrocarbon group, a C₁₋₂₀ halogenated hydrocarbon group,an oxygen-containing group, a sulfur-containing group, asilicon-containing group or a nitrogen-containing group. When p is 2 ormore, a plurality of groups represented by Xs may be the same ordifferent.

The halogen atom, C₁₋₂₀ hydrocarbon group, C₁₋₂₀ halogenated hydrocarbongroup, oxygen-containing group, sulfur-containing group,silicon-containing group and nitrogen-containing group represented by Xin formula (IX) includes, for example, the halogen atom, hydrocarbongroup, halogenated hydrocarbon group, oxygen-containing group,sulfur-containing group, silicon-containing group andnitrogen-containing group illustrated as R¹ to R⁷ in the general formula(I) above.

Specific examples of the compounds represented by the general formula(IX) above are shown below:

Compound (a-9)

As the component (A) in the present invention, compound (a-9)represented by the following general formula (X) can be used.

In formula (X), M is a transition metal atom selected from the groups 3to 11 in the periodic table, preferably a transition metal atom selectedfrom the groups 3 to 6 in the periodic table, more preferably atransition metal atom selected from the group 4 in the periodic table.Specifically, M is scandium, yttrium, titanium, zirconium, hafnium,vanadium, niobium, tantalum, chromium, molybdenum or tungsten,preferably titanium, zirconium or hafnium.

In formula (X), A represents an atom selected from the groups 14 to 16in the periodic table, preferably an atom selected from the groups 15and 16. Specifically, A is preferably NR⁹, PR¹⁰, O or S.

In formula (X), m is an integer of 0 to 3, n is an integer of 0 or 1, pis an integer of 1 to 3, and q is a number satisfying the valence of M,and when m is 0, n is 0, and p is preferably 2.

In formula (X), R¹ to R¹⁰ may be the same or different and eachrepresent a hydrogen atom, a halogen atom, a C₁₋₂₀ hydrocarbon group, aC₁₋₂₀ halogenated hydrocarbon group, an oxygen-containing group, asulfur-containing group, a silicon-containing group or anitrogen-containing group, and two or more of these groups may be boundto each other to form a ring.

The halogen atom, C₁₋₂₀ hydrocarbon group, C₁₋₂₀ halogenated hydrocarbongroup, oxygen-containing group, sulfur-containing group,silicon-containing group and nitrogen-containing group represented by R¹to R¹⁰ in formula (X) include, for example, the halogen atom,hydrocarbon group, halogenated hydrocarbon group, oxygen-containinggroup, sulfur-containing group, silicon-containing group andnitrogen-containing group illustrated as R¹ to R⁷ in the general formula(I) above.

In formula (X), X represents a hydrogen atom, a halogen atom, an oxygenatom, a C₁₋₂₀ hydrocarbon group, a C₁₋₂₀ halogenated hydrocarbon group,an oxygen-containing group, a sulfur-containing group, asilicon-containing group or a nitrogen-containing group. Note that whenq is 2 or more, a plurality of groups represented by Xs may be the sameor different.

The halogen atom, C₁₋₂₀ hydrocarbon group, C₁₋₂₀ halogenated hydrocarbongroup, oxygen-containing group, sulfur-containing group,silicon-containing group and nitrogen-containing group represented by Xin formula (X) include, for example, the halogen atom, hydrocarbongroup, halogenated hydrocarbon group, oxygen-containing group,sulfur-containing group, silicon-containing group andnitrogen-containing group illustrated as R¹ to R⁷ in the general formula(I) above.

When m in formula (X) is 1 to 3, Y is a group for bridging a boratebenzene ring with A, and represents carbon, silicon or germanium.

Examples of compounds represented by the general formula (X) are shownbelow.

In the above-illustrated compounds, ^(i)Pr indicates an isopropyl group,^(t)Bu indicates a tert-butyl group, and Ph indicates a phenyl group.

Compound (a-10)

As the component (A) in the present invention, compound (a-10)represented by the following general formula (XIa) can be used.

In formula (XIa), M is a transition metal atom selected from the groups3 to 11 in the periodic table, preferably a transition metal atom in thegroups 3 to 6 in the periodic table, more preferably a transition metalatom in the groups 4 and 5 in the periodic table, still more preferablya transition metal atom in the group 4 in the periodic table.Specifically, M is scandium, yttrium, titanium, zirconium, hafnium,vanadium, niobium, tantalum, chromium, molybdenum or tungsten,preferably titanium, zirconium or hafnium.

In formula (XIa), A and A′ may be the same or different and eachrepresent a C₁₋₅₀ hydrocarbon group, a C₁₋₅₀ halogenated hydrocarbongroup, a hydrocarbon group having an oxygen-containing group, asulfur-containing group or a silicon-containing group, or a halogenatedhydrocarbon group having an oxygen-containing group, a sulfur-containinggroup or a silicon-containing group, preferably a hydrocarbon, morepreferably an aryl group substituted with an alkyl group.

The C₁₋₅₀ hydrocarbon group and C₁₋₅₀ halogenated hydrocarbon grouprepresented by A and A′ in formula (XIa) include, for example, thehydrocarbon group and halogenated hydrocarbon group illustrated as R¹ toR⁷ in the general formula (I) above; the hydrocarbon group having anoxygen-containing group, a sulfur-containing group or asilicon-containing group, represented by A and A′ includes, for example,the hydrocarbon group having an oxygen-containing group, asulfur-containing group or a silicon-containing group illustrated as R¹to R⁷ in the general formula (I) above; and the halogenated hydrocarbongroup having an oxygen-containing group, a sulfur-containing group or asilicon-containing group represented by A and A′ includes, for example,the halogenated hydrocarbon group having an oxygen-containing group, asulfur-containing group or a silicon-containing group illustrated as R¹to R⁷ in the general formula (I) above.

In formula (XIa), D may be present or absent, and when D is present, itis a linking group for bridging A to A′, and when D is absent, A and A′are bound to each other via —O-M-O— only.

D in formula (XIa) is specifically a single bond, a C₁₋₂₀ hydrocarbongroup, a C₁₋₂₀ halogenated hydrocarbon, an oxygen atom, a sulfur atom ora group represented by R¹R²Z. R¹ and R² may be the same or different andeach represent a C₁₋₂₀ hydrocarbon group or a C₁₋₂₀ hydrocarbon groupcontaining at least one heteroatom, and may be bound to each other toform a ring, and Z represents a carbon atom, a nitrogen atom, a sulfuratom, a phosphorus atom or a silicon atom.

In formula (XIa), n is a number satisfying the valence of M, and isspecifically an integer of 1 to 5, preferably 1 to 4, more preferably 1to 3.

In formula (XIa), X represents a hydrogen atom, a halogen atom, a C₁₋₂₀hydrocarbon group, a C₁₋₂₀ halogenated hydrocarbon group, anoxygen-containing group, a sulfur-containing group, a silicon-containinggroup or a nitrogen-containing group, and when n is 2 or more, aplurality of groups represented by Xs may be the same or different, anda plurality of groups represented by Xs may be bound to each other toform a ring.

The halogen atom, C₁₋₂₀ hydrocarbon group, C₁₋₂₀ halogenated hydrocarbongroup, oxygen-containing group, sulfur-containing group,silicon-containing group and nitrogen-containing group represented by Xin formula (XIa) include, for example, the halogen atom, hydrocarbongroup, halogenated hydrocarbon group, oxygen-containing group,sulfur-containing group, silicon-containing group andnitrogen-containing group illustrated as R¹ to R⁷ in the general formula(I) above.

Examples of compounds represented by the general formula (XIa) are shownbelow.

In the above-illustrated compounds, tBu indicates a t-butyl group, andMe indicates a methyl group.

Compound (a-11)

As the component (A) in the present invention, compound (a-11)represented by the following general formula (XIb) can be used.

In formula (XIb), M represents a transition metal atom selected from thegroups 3 to 11 in the periodic table, preferably a transition metal atomin the groups 3 to 6 in the periodic table, more preferably a transitionmetal atom in the groups 4 and 5 in the periodic table, still morepreferably a transition metal atom in the group 4 in the periodic table.Specifically, M is scandium, yttrium, titanium, zirconium, hafnium,vanadium, niobium, tantalum, chromium, molybdenum or tungsten, morepreferably titanium, zirconium or hafnium.

In formula (XIb), m is an integer of 1 to 6, preferably an integer of 1to 4, more preferably an integer of 1 to 3, still more preferably aninteger of 1 to 2.

In formula (XIb), A and A′ may be the same or different and eachrepresent a C₁₋₅₀ hydrocarbon group, a C₁₋₅₀ halogenated hydrocarbongroup, a hydrocarbon group containing an oxygen-containing group, asulfur-containing group or a silicon-containing group, or a halogenatedgroup containing an oxygen-containing group, a sulfur-containing groupor a silicon-containing group, preferably a hydrocarbon group, morepreferably an aryl group substituted with an alkyl group.

The C₁₋₅₀ hydrocarbon group and C₁₋₅₀ halogenated hydrocarbon grouprepresented by A and A′ in formula (XIb) includes, for example, thehydrocarbon group and halogenated hydrocarbon group illustrated as R¹ toR⁷ in the general formula (I) above; the hydrocarbon group containing anoxygen-containing group, a sulfur-containing group or asilicon-containing group represented by A and A′ includes, for example,the hydrocarbon group containing an oxygen-containing group, asulfur-containing group or a silicon-containing group illustrated as R¹to R⁷ in the general formula (I) above; and the halogenated hydrocarbongroup containing an oxygen-containing group, a sulfur-containing groupor a silicon-containing group represented by A and A′ includes, forexample, the halogenated hydrocarbon group containing anoxygen-containing group, a sulfur-containing group or asilicon-containing group illustrated as R¹ to R⁷ in the general formula(I) above.

In formula (XIb), D may be present or absent, and when D is present, itis a linking group for bridging A to A′, and when D is absent, A and A′are bound to each other via —O-M-O— only. D is specifically a singlebond, a C₁₋₂₀ hydrocarbon group, a C₁₋₂₀ halogenated hydrocarbon, anoxygen atom, a sulfur atom or a group represented by R¹R²Z. R¹ and R²may be the same or different and each represent a C₁₋₂₀ hydrocarbongroup or a C₁₋₂₀ hydrocarbon group containing at least one heteroatom,and may be bound to each other to form a ring, and Z represents a carbonatom, a nitrogen atom, a sulfur atom, a phosphorus atom or a siliconatom.

In formula (XIb), n is a number satisfying the valence of M, and isspecifically an integer of 1 to 5, preferably 1 to 4, more preferably 1to 3.

When n in formula (XIb) is 1, X is an oxygen atom, and when n is 2 ormore, at least one of Xs is an oxygen atom, and other Xs represent ahydrogen atom, a halogen atom, an oxygen atom, a C₁₋₂₀ hydrocarbongroup, a C₁₋₂₀ halogenated hydrocarbon group, an oxygen-containinggroup, a sulfur-containing group, a silicon-containing group or anitrogen-containing group, and when there are a plurality of groupsrepresented by Xs, a plurality of groups represented by Xs may be thesame or different, and a plurality of groups represented by Xs may bebound to each other to form a ring.

The halogen atom, C₁₋₂₀ hydrocarbon group, C₁₋₂₀ halogenated hydrocarbongroup, oxygen-containing group, sulfur-containing group,silicon-containing group and nitrogen-containing group represented by Xin formula (XIb) include, for example, the halogen atom, hydrocarbongroup, halogenated hydrocarbon group, oxygen-containing group,sulfur-containing group, silicon-containing group andnitrogen-containing group illustrated as R¹ to R⁷ in the general formula(I) above.

Compound (a-12)

As the component (A) in the present invention, compound (a-12)represented by the following general formula (XII) can be used.

In formula (XII), M represents a transition metal atom in the groups 3to 11 in the periodic table, preferably a transition metal atom in thegroups 3 to 6 in the periodic table, more preferably a transition metalatom in the group 4 in the periodic table. Specifically, M is scandium,yttrium, titanium, zirconium, hafnium, vanadium, niobium, tantalum,chromium, molybdenum or tungsten, more preferably titanium, zirconium orhafnium.

Ys may be the same or different and each represent an atom in the groups13 to 15 in the periodic table, and specifically Y represents carbon,silicon, germanium, nitrogen, phosphorus, oxygen or sulfur. At least oneof Ys is an atom other than carbon.

In formula (XII), m is an integer of 1 to 6, preferably 1 to 4, morepreferably 1 to 3.

In formula (XII), R¹ to R⁵ are present when their bound Ys are each anatom selected from the group 14 in the periodic table, and R¹ to R⁵ maybe the same or different and each represent a hydrogen atom, a halogenatom, a hydrocarbon group, a halogenated hydrocarbon group, an organicsilyl group, or a hydrocarbon group substituted with a substituent groupcontaining at least one atom selected from nitrogen, oxygen, phosphorus,sulfur and silicon, and two or more of these groups may be bound to eachother to form a ring.

The hydrocarbon group and halogenated hydrocarbon group represented byR¹ to R⁵ in formula (XII) include, for example, the hydrocarbon groupand halogenated hydrocarbon group illustrated as R¹ to R⁷ in the generalformula (I) above; the organic silyl group represented by R¹ to R⁵includes, for example, the silicon-containing group illustrated as R¹ toR⁷ in the general formula (I) above; and the substituent group having atleast one atom selected from nitrogen, oxygen, phosphorus, sulfur andsilicon represented by R¹ to R⁵ includes, for example, the nitrogen-,oxygen-, phosphorus-, sulfur- or nitrogen-containing residue out of thenitrogen-containing group, oxygen-containing group, sulfur-containinggroup and heterocyclic compound residue illustrated as R¹ to R⁷ in thegeneral formula (I) above.

In formula (XII), n is a number satisfying the valence of M, and isspecifically an integer of 1 to 5, preferably 1 to 4, more preferably 1to 3.

In formula (XII), X represents a hydrogen atom, a halogen atom, anoxygen atom, a C₁₋₂₀ hydrocarbon group, a C₁₋₂₀ halogenated hydrocarbongroup, an oxygen-containing group, a sulfur-containing group, asilicon-containing group or a nitrogen-containing group, and when n is 2or more, a plurality of groups represented by Xs may be the same ordifferent, and a plurality of groups represented by Xs may be bound toeach other to form a ring.

The halogen atom, C₁₋₂₀ hydrocarbon group, C₁₋₂₀ halogenated hydrocarbongroup, oxygen-containing group, sulfur-containing group,silicon-containing group and nitrogen-containing group represented by Xin formula (XII) include, for example, the halogen atom, hydrocarbongroup, halogenated hydrocarbon group, oxygen-containing group,sulfur-containing group, silicon-containing group andnitrogen-containing group illustrated as R¹ to R⁶ in the general formula(I) above.

Examples of compounds represented by the general formula (XII) above areshown below.

In the above-illustrated compounds, ^(t)Bu indicates a tert-butyl group,and Me indicates a methyl group.

Compound (a-13)

As the component (A) in the present invention, compound (a-13)represented by the following general formula (XIII) can be used.

In formula (XIII), M is a transition metal compound in the groups 3 to11 in the periodic table, preferably a transition metal atom in thegroups 4 to 5. Specifically, M is titanium, zirconium, vanadium, niobiumor tantalum.

In formula (XIII), m is an integer of 1 to 6, preferably 1 to 3.

In formula (XIII), Rs may be the same or different and each represent ahydrogen atom, a C₁₋₂₀ hydrocarbon group and a C₁₋₂₀ halogenatedhydrocarbon group, and two or more of these groups may be bound to eachother to form a ring.

In formula (XIII), n is a number satisfying the valence of M, and isspecifically an integer of 1 to 5, preferably 1 to 4, more preferably 1to 3.

In formula (XIII), when n is 1, X is an oxygen atom, and when n is 2 ormore, at least one of Xs is an oxygen atom, and other Xs represent ahydrogen atom, a halogen atom, an oxygen atom, a C₁₋₂₀ hydrocarbongroup, a C₁₋₂₀ halogenated hydrocarbon group, an oxygen-containinggroup, a sulfur-containing group, a silicon-containing group or anitrogen-containing group. When there are a plurality of groupsrepresented by Xs, a plurality of groups represented by Xs may be thesame or different, and a plurality of groups represented by Xs may bebound to each other to form a ring.

The halogen atom, C₁₋₂₀ hydrocarbon group, C₁₋₂₀ halogenated hydrocarbongroup, oxygen-containing group, sulfur-containing group,silicon-containing group and nitrogen-containing group represented by Xin formula (XIII) include, for example, the halogen atom, hydrocarbongroup, halogenated hydrocarbon group, oxygen-containing group,sulfur-containing group, silicon-containing group andnitrogen-containing group illustrated as R¹ to R⁷ in the general formula(I) above.

In formula (XIII), Y may be present or absent, and when Y is present, itis the group 15 or 16 atom in the periodic table, specifically O, S, Seor NR.

The specific structures of these compounds include, but are not limitedto, the followings:

Compound (a-14)

As the component (A) in the present invention, compound (a-14)represented by the following general formula (XIVa) can be used.

In formula (XIVa), M is a transition metal atom selected from the groups3 to 7 and 11 in the periodic table, preferably a transition metal atomselected from the groups 4 and 5.

In formula (XIVa), R¹ to R⁴ may be the same or different and eachrepresent a C₁₋₅₀ hydrocarbon group, a C₁₋₅₀ halogenated hydrocarbongroup, an organic silyl group, or a hydrocarbon group substituted with asubstituent group having at least one atom selected from nitrogen,oxygen, phosphorus, sulfur and silicon. Two or more groups out of thegroups represented by R¹ to R⁴, preferably adjacent groups, may be boundto each other to form a ring.

The C₁₋₅₀ hydrocarbon group and C₁₋₅₀ halogenated hydrocarbon grouprepresented by R¹ to R⁴ in formula (XIVa) include, for example, thehydrocarbon group and halogenated hydrocarbon group illustrated as R¹ toR⁷ in the general formula (I) above; the organic silyl group representedby R¹ to R⁴ includes, for example, the silicon-containing groupillustrated as R¹ to R⁷ in the general formula (I) above; and thesubstituent group having at least one atom selected from nitrogen,oxygen, phosphorus, sulfur and silicon represented by R¹ to R⁴ includes,for example, the nitrogen-, oxygen-, phosphorus-, sulfur- orsilicon-containing residue out of the nitrogen-containing group,oxygen-containing group, sulfur-containing group and heterocycliccompound residue illustrated as R¹ to R⁷ in the general formula (I)above.

In formula (XIVa) n is a number satisfying the valence of M, and isspecifically an integer of 0 to 4.

In formula (XIVa), X represents a hydrogen atom, a halogen atom, a C₁₋₂₀hydrocarbon group, a C₁₋₂₀ halogenated hydrocarbon group, anoxygen-containing group, a sulfur-containing group, a silicon-containinggroup or a nitrogen-containing group, and when n is 2 or more, aplurality of groups represented by Xs may be the same or different.

The halogen atom, C₁₋₂₀ hydrocarbon group, C₁₋₂₀ halogenated hydrocarbongroup, oxygen-containing group, sulfur-containing group,silicon-containing group and nitrogen-containing group represented by Xin formula (XIVa) include, for example, the halogen atom, hydrocarbongroup, halogenated hydrocarbon group, oxygen-containing group,sulfur-containing group, silicon-containing group andnitrogen-containing group illustrated as R¹ to R⁷ in the general formula(I) above.

Compound (a-15)

As the component (A) in the present invention, compound (a-15)represented by the following general formula (XIVb) can be used.

In formula (XIVb), M is a transition metal atom selected from the groups8 to 10 in the periodic table, preferably nickel, palladium or platinum.

In formula (XIVb), R¹ to R⁴ may be the same or different and eachrepresent a C₁₋₅₀ hydrocarbon group, a C₁₋₅₀ halogenated hydrocarbongroup, an organic silyl group, or a hydrocarbon group substituted with asubstituent group having at least one atom selected from nitrogen,oxygen, phosphorus, sulfur and silicon. Two or more groups out of thegroups represented by R¹ to R⁴, preferably adjacent groups, may be boundto each other to form a ring.

The C₁₋₅₀ hydrocarbon group and C₁₋₅₀ halogenated hydrocarbon grouprepresented by R¹ to R⁴ in formula (XIVb) include, for example, thehydrocarbon group and halogenated hydrocarbon group illustrated as R¹ toR⁷ in the general formula (I) above; the organic silyl group representedby R¹ to R⁴ includes, for example, the silicon-containing groupillustrated as R¹ to R⁷ in the general formula (I) above; and thesubstituent group having at least one atom selected from nitrogen,oxygen, phosphorus, sulfur and silicon represented by R¹ to R⁴ includes,for example, the nitrogen-, oxygen-, phosphorus-, sulfur- orsilicon-containing residue out of the nitrogen-containing group,oxygen-containing group, sulfur-containing group and heterocycliccompound residue illustrated as R¹ to R⁷ in the general formula (I)above.

In formula (XIVb), n is a number satisfying the valence of M, and isspecifically an integer of 0 to 4.

In formula (XIVb), X represents a hydrogen atom, a halogen atom, a C₁₋₂₀hydrocarbon group, a C₁₋₂₀ halogenated hydrocarbon group, anoxygen-containing group, a sulfur-containing group, a silicon-containinggroup or a nitrogen-containing group, and when n is 2 or more, aplurality of groups represented by Xs may be the same or different.

The halogen atom, C₁₋₂₀ hydrocarbon group, C₁₋₂₀ halogenated hydrocarbongroup, oxygen-containing group, sulfur-containing group,silicon-containing group and nitrogen-containing group represented by Xin formula (XIVb) include, for example, the halogen atom, hydrocarbongroup, halogenated hydrocarbon group, oxygen-containing group,sulfur-containing group, silicon-containing group andnitrogen-containing group illustrated as R¹ to R⁷ in the general formula(I) above.

The specific structures of these compounds are shown below:

Compound (a-16)

As the component (A) in the present invention, compound (a-16)represented by the following general formula (XIVc) can be used.

In formula (XIVc), M is a transition metal atom selected from the groups3 to 10 in the periodic table, preferably nickel, palladium or platinum.

In formula (XIVc), m is an integer of 1 to 6, preferably an integer of 1to 4, more preferably an integer of 1 to 3, still more preferably aninteger of 1 to 2.

In formula (XIVc), R¹ to R⁴ may be the same or different and eachrepresent a C₁₋₅₀ hydrocarbon group, a C₁₋₅₀ halogenated hydrocarbongroup, an organic silyl group, or a hydrocarbon group substituted with asubstituent group containing at least one atom selected from nitrogen,oxygen, phosphorus, sulfur and silicon. Two or more groups out of thegroups represented by R¹ to R⁴, preferably adjacent groups, may be boundto each other to form a ring.

The C₁₋₅₀ hydrocarbon group and C₁₋₅₀ halogenated hydrocarbon grouprepresented by R¹ to R⁴ in formula (XIVc) include, for example, thehydrocarbon group and halogenated hydrocarbon group illustrated as R¹ toR⁷ in the general formula (I) above; the organic silyl group representedby R¹ to R⁴ includes, for example, the silicon-containing groupillustrated as R¹ to R⁷ in the general formula (I) above; and thesubstituent group having at least one atom selected from nitrogen,oxygen, phosphorus, sulfur and silicon represented by R¹ to R⁴ includes,for example, the nitrogen-, oxygen-, phosphorus-, sulfur- orsilicon-containing residue out of the nitrogen-containing group,oxygen-containing group, sulfur-containing group and heterocycliccompound residue illustrated as R¹ to R⁷ in the general formula (I)above.

In formula (XIVc), n is a number satisfying the valence of M, and isspecifically an integer of 1 to 5, preferably 1 to 4, more preferably 1to 3.

In formula (XIVc), when n is 1, X is an oxygen atom, and when n is 2 ormore, at least one of Xs is an oxygen atom, and other Xs represent ahydrogen atom, a halogen atom, an oxygen atom, a C₁₋₂₀ hydrocarbongroup, a C₁₋₂₀ halogenated hydrocarbon group, an oxygen-containinggroup, a sulfur-containing group, a silicon-containing group or anitrogen-containing group, and when there are a plurality of groupsrepresented by Xs, a plurality of groups represented by Xs may be thesame or different.

The halogen atom, C₁₋₂₀ hydrocarbon group, C₁₋₂₀ halogenated hydrocarbongroup, oxygen-containing group, sulfur-containing group,silicon-containing group and nitrogen-containing group represented by Xin formula (XIVc) include, for example, the halogen atom, hydrocarbongroup, halogenated hydrocarbon group, oxygen-containing group,sulfur-containing group, silicon-containing group andnitrogen-containing group illustrated as R¹ to R⁶ in the general formula(IVa) above.

Compound (a-17)

As the component (A) in the present invention, compound (a-17)represented by the following general formula (XV) can be used.

In formula (XV), Y¹ and Y³ may be the same or different and eachrepresent an atom selected from the group 15 in the periodic table.

In formula (XV), Y² represents an atom selected from the group 16 in theperiodic table.

In formula (XV), R¹ to R⁸ may be the same or different and eachrepresent a hydrogen atom, a halogen atom, a C₁₋₂₀ hydrocarbon group, aC₁₋₂₀ halogenated hydrocarbon group, an oxygen-containing group, asulfur-containing group or a silicon-containing group, and two or moreof these groups may be bound to each other to form a ring.

The C₁₋₂₀ hydrocarbon group and C₁₋₂₀ halogenated hydrocarbon grouprepresented by R¹ to R⁸ in formula (XV) include, for example, thehydrocarbon group and halogenated hydrocarbon group illustrated as R¹ toR⁷ in the general formula (I) above, and the halogen atom,oxygen-containing group, sulfur-containing group and silicon-containinggroup represented by R¹ to R⁸ include, for example, the halogen atom,oxygen-containing group, sulfur-containing group and silicon-containinggroup illustrated as R¹ to R⁷ in the general formula (I) above.

Compound (a-18)

As the component (A) in the present invention, compound (a-18)represented by the following general formula (XVI) can be used.

In formula (XVI), M represents a transition metal atom selected from thegroups 3 to 11 in the periodic table, preferably a transition metal atomin the groups 3 to 6 and 8 to 10, more preferably a transition metalatom in the group 4, 5 or 6, still more preferably a metal atom in thegroup 4 or 5.

In formula (XVI), m is an integer of 1 to 6, preferably an integer of 1to 4, more preferably an integer of 1 to 3, still more preferably aninteger of 1 to 2.

In formula (XVI), A represents an oxygen atom, a sulfur atom or asubstituent —R⁵-containing nitrogen atom (—N(R⁵)—)

In formula (XVI), D represents —C(R⁶) (R⁷), Si(R⁸) (R⁹)—, —P(O)(R¹⁰)—,—P(R¹¹)—, —SO— or —S—.

In formula (XVI), Z represents N-binding —R¹² and —R¹³, ═C(R¹⁴)R¹⁵ or═NR¹⁶.

In formula (XVI), R¹ to R¹⁶ may be the same or different and eachrepresent a hydrogen atom, a halogen atom, a hydrocarbon group, anoxygen-containing group, a nitrogen-containing group, a boron-containinggroup, a sulfur-containing group, a phosphorus-containing group, aheterocyclic compound residue, a silicon-containing group, agermanium-containing group or a tin-containing group, and two or more ofthese groups may be bound to one another to form a ring, and when m is 2or more, two groups out of the groups represented by R¹ to R¹⁶ may bebound to each other.

The halogen atom, hydrocarbon group, oxygen-containing group,nitrogen-containing group, boron-containing group, sulfur-containinggroup, phosphorus-containing group, heterocyclic compound residue,silicon-containing group, germanium-containing group and tin-containinggroup represented by R¹ to R¹⁶ n formula (XVI) include, for example, thesame atom or group illustrated as R¹ to R⁷ in the general formula (I)above.

In formula (XVI), n is a number satisfying the valence of M, and isspecifically an integer of 1 to 5, preferably 1 to 4, more preferably 1to 3.

In formula (XVI), X represents a hydrogen atom, a halogen atom, anoxygen atom, a hydrocarbon group, an oxygen-containing group, asulfur-containing group, a nitrogen-containing group, a boron-containinggroup, an aluminum-containing group, a phosphorus-containing group, ahalogen-containing group, a heterocyclic compound residue, asilicon-containing group, a germanium-containing group or atin-containing group, and when n is 2 or more, a plurality of groupsrepresented by Xs may be the same or different, and a plurality ofgroups represented by Xs may be bound to each other to form a ring.

The halogen atom, hydrocarbon group, oxygen-containing group,sulfur-containing group, nitrogen-containing group, boron-containinggroup, aluminum-containing group, phosphorus-containing group,halogen-containing group, heterocyclic compound residue,silicon-containing group, germanium-containing group and tin-containinggroup represented by X in formula (XVI) include, for example, the sameatom or group illustrated as X¹ in the general formula (I) above.

Compound (a-19)

As the component (A) in the present invention, compound (a-19)represented by the following general formula (XVII) or (XVIII) can beused.

In formulae (XVII) and (XVIII), M represents a transition metal atomselected from the groups 3 to 11 in the periodic table, preferably atransition metal atom in the groups 3 to 6 and 8 to 10, more preferablya transition metal atom in the group 4, 5 or 6, still more preferably ametal atom in the group 4 or 5.

In formula (XVII), m is an integer of 1 to 3.

In formula (XVIII), m′ is an integer of 1 to 6, preferably an integer of1 to 4, more preferably an integer of 1 to 3, still more preferably aninteger of 1 to 2.

In formulae (XVII) and (XVIII), E represents a nitrogen atom or asubstituent —R⁵-containing carbon atom (—C(R⁵)═).

In formulae (XVII) and (XVIII), G represents an oxygen atom, a sulfuratom or a substituent —R⁶-containing nitrogen atom (—N(R⁶)—).

In formulae (XVII) and (XVIII), R¹ to R⁶ may be the same or differentand each represent a hydrogen atom, a halogen atom, a hydrocarbon group,an oxygen-containing group, a nitrogen-containing group, aboron-containing group, a sulfur-containing group, aphosphorus-containing group, a heterocyclic compound residue, asilicon-containing group, a germanium-containing group or atin-containing group, and two or more of these groups may be bound toone another to form a ring, and when m in formula (XVII) is 2 or more,two groups out of the groups represented by R¹ to R⁶ may be bound toeach other, and when m′ in formula (XVIII) is 2 or more, two groups outof the groups represented by R¹ to R⁶ may be bound to each other.

The halogen atom, hydrocarbon group, oxygen-containing group,nitrogen-containing group, boron-containing group, sulfur-containinggroup, phosphorus-containing group, heterocyclic compound residue,silicon-containing group, germanium-containing group and tin-containinggroup represented by R¹ to R⁶ in formulae (XVII) and (XVIII) include,for example, the same atom or group illustrated as R¹ to R⁷ in thegeneral formula (I) above.

In formulae (XVII) and (XVIII), n is a number satisfying the valence ofM, and is specifically an integer of 1 to 5, preferably 1 to 4, morepreferably 1 to 3.

In formulae (XVII) and (XVIII), X represents a hydrogen atom, a halogenatom, an oxygen atom, a hydrocarbon group, an oxygen-containing group, asulfur-containing group, a nitrogen-containing group, a boron-containinggroup, an aluminum-containing group, a phosphorus-containing group, ahalogen-containing group, a heterocyclic compound residue, asilicon-containing group, a germanium-containing group or atin-containing group, and when n in formulae (XVII) and (XVIII) is 2 ormore, a plurality of groups represented by Xs may be the same ordifferent, and a plurality of groups represented by Xs may be bound toeach other to form a ring.

The halogen atom, hydrocarbon group, oxygen-containing group,sulfur-containing group, nitrogen-containing group, boron-containinggroup, aluminum-containing group, phosphorus-containing group,halogen-containing group, heterocyclic compound residue,silicon-containing group, germanium-containing group and tin-containinggroup represented by X in formulae (XVII) and (XVIII) include, forexample, the same atom or group illustrated as R¹ to R⁷ in the generalformula (I) above.

Compound (a-20)

As the component (A) in the present invention, compound (a-20)represented by the following general formula (XIX) can be used.

In formula (XIX), M represents a transition metal atom selected from thegroups 3 to 11 in the periodic table, preferably a transition metal atomin the groups 3 to 6 and 8 to 10, more preferably a transition metalatom in the group 4, 5 or 6, still more preferably a metal atom in thegroup 4 or 5.

In formula (XIX), m is an integer of 1 to 6, preferably an integer of 1to 4, more preferably an integer of 1 to 3, still more preferably aninteger of 1 to 2.

In formula (XIX), A represents an oxygen atom, a sulfur atom or asubstituent —R⁵-containing nitrogen atom (—N(R⁵)—).

In formula (XIX), B represents N-binding —R⁶ and —R⁷, ═C(R⁸)R⁹ or ═NR¹⁰.

In formula (XIX), R¹ to R¹⁰ may be the same or different and eachrepresent a hydrogen atom, a halogen atom, a hydrocarbon group, anoxygen-containing group, a nitrogen-containing group, a boron-containinggroup, a sulfur-containing group, a phosphorus-containing group, aheterocyclic compound residue, a silicon-containing group, agermanium-containing group or a tin-containing group, and two or more ofthese groups may be bound to each other to form a ring. When m is 2 ormore, one group out of R¹ to R¹⁰ contained in one ligand may be bound toone group out of R¹ to R¹⁰ contained in another ligand, and R¹s, R²s,R³s, R⁴s, R⁵s, R⁵s, R⁷s, R⁸s, R⁹s or R¹⁰s may be the same or different.

The halogen atom, hydrocarbon group, oxygen-containing group,nitrogen-containing group, boron-containing group, sulfur-containinggroup, phosphorus-containing group, heterocyclic compound residue,silicon-containing group, germanium-containing group and tin-containinggroup represented by R¹ to R¹⁰ in formula (XIX) include, for example,the same atom or group illustrated as R¹ to R⁷ in the general formula(I) above.

In formula (XIX), n is a number satisfying the valence of M, and isspecifically an integer of 1 to 5, preferably 1 to 4, more preferably 1to 3.

In formula (XIX), X represents a hydrogen atom, a halogen atom, anoxygen atom, a hydrocarbon group, an oxygen-containing group, asulfur-containing group, a nitrogen-containing group, a boron-containinggroup, an aluminum-containing group, a phosphorus-containing group, ahalogen-containing group, a heterocyclic compound residue, asilicon-containing group, a germanium-containing group or atin-containing group, and when n is 2 or more, a plurality of groupsrepresented by Xs may be the same or different, and a plurality ofgroups represented by Xs may be bound to each other to form a ring.

The halogen atom, hydrocarbon group, halogenated hydrocarbon group,oxygen-containing group, sulfur-containing group, nitrogen-containinggroup, boron-containing group, aluminum-containing group,phosphorus-containing group, halogen-containing group, heterocycliccompound residue, silicon-containing group, germanium-containing groupand tin-containing group represented by X in formula (XIX) include, forexample, the same atom or group illustrated as X¹ in the general formula(I) above.

Compound (a-21)

As the component (A) in the present invention, compound (a-21)represented by the following general formula (XXa) or (XXIa) can beused.

In formulae (XXa) and (XXIa), M represents a transition metal atomselected from the groups 3 and 4 in the periodic table.

In formulae (XXa) and (XXIa), A¹ represents an oxygen atom, a sulfuratom or a hydrocarbon-substituted nitrogen atom.

In formulae (XXa) and (XXIa), A² represents a hydrocarbon-substitutedoxygen atom, a hydrocarbon-substituted sulfur atom or ahydrocarbon-substituted nitrogen atom.

In formulae (XXa) and (XXIa), E represents an oxygen atom or a sulfuratom.

In formulae (XXa) and (XXIa), m is an integer of 1 to 2.

In formulae (XXa) and (XXIa), R¹ to R⁵ may be the same or different andeach represent a hydrogen atom, a hydrocarbon group or ahydrocarbon-substituted silyl group.

In formulae (XXa) and (XXIa), n is a number satisfying the valence of M,and is specifically an integer of 0 to 5, preferably 0 to 4, morepreferably 0 to 3.

In formulae (XXa) and (XXIa), X represents a hydrogen atom, a halogenatom, an oxygen atom, a hydrocarbon group, an oxygen-containing group, asulfur-containing group, a nitrogen-containing group, a boron-containinggroup, an aluminum-containing group, a phosphorus-containing group, ahalogen-containing group, a heterocyclic compound residue, asilicon-containing group, a germanium-containing group or atin-containing group, and when n is 2 or more, a plurality of groupsrepresented by Xs may be the same or different, and a plurality ofgroups represented by Xs may be bound to each other to form a ring.

The halogen atom, hydrocarbon group, oxygen-containing group,sulfur-containing group, nitrogen-containing group, boron-containinggroup, aluminum-containing group, phosphorus-containing group,halogen-containing group, heterocyclic compound residue,silicon-containing group, germanium-containing group and tin-containinggroup represented by X in formulae (XXa) and (XXIa) include, forexample, the same atom or group illustrated as X¹ in the general formula(I) above.

Compound (a-22)

As the component (A) in the present invention, compound (a-22)represented by the following general formula (XXb) or (XXIb) can beused.

In formulae (XXb) and (XXIb), M represents a transition metal atomselected from the groups 5 to 11 in the periodic table, preferably atransition metal atom in the groups 8 to 10 in the periodic table.

In formulae (XXb) and (XXIb), A¹ represents an oxygen atom, a sulfuratom or a hydrocarbon-substituted nitrogen atom.

In formulae (XXb) and (XXIb), A² represents a hydrocarbon-substitutedoxygen atom, a hydrocarbon-substituted sulfur atom or ahydrocarbon-substituted nitrogen atom.

In formulae (XXb) and (XXIb), E represents an oxygen atom or a sulfuratom.

In formulae (XXb) and (XXIb), m is an integer of 1 to 2.

In formulae (XXb) and (XXIb), R¹ to R⁵ may be the same or different andeach represent a hydrogen atom, a hydrocarbon group or ahydrocarbon-substituted silyl group.

In formulae (XXb) and (XXIb), n is a number satisfying the valence of M,and is specifically an integer of 1 to 5, preferably 1 to 4, morepreferably 1 to 3.

In formulae (XXb) and (XXIb), X represents a hydrogen atom, a halogenatom, an oxygen atom, a hydrocarbon group, an oxygen-containing group, asulfur-containing group, a nitrogen-containing group, a boron-containinggroup, an aluminum-containing group, a phosphorus-containing group, ahalogen-containing group, a heterocyclic compound residue, asilicon-containing group, a germanium-containing group or atin-containing group, and when n is 2 or more, a plurality of groupsrepresented by Xs may be the same or different, and a plurality ofgroups represented by Xs may be bound to each other to form a ring.

The halogen atom, hydrocarbon group, oxygen-containing group,sulfur-containing group, nitrogen-containing group, boron-containinggroup, aluminum-containing group, phosphorus-containing group,halogen-containing group, heterocyclic compound residue,silicon-containing group, germanium-containing group and tin-containinggroup represented by X in formulae (XXb) and (XXIb) include, forexample, the same atom or group illustrated as X¹ in the general formula(I) above.Compound (a-23) As the component (A) in the present invention, compound(a-23) represented by the following general formula (XXII), (XXIII),(XXIV) or (XXV) can be used.

In formulae (XXII), (XXIII), (XXIV) and (XXV), M represents a transitionmetal atom selected from the groups 3 to 11 in the periodic table,preferably a transition metal atom in the groups 3 to 6 and 8 to 10,more preferably a transition metal atom in the group 4, 5 or 6, stillmore preferably a metal atom in the group 4 or 5.

In formulae (XXII), (XXIII), (XXIV) and (XXV), A represents an oxygenatom, a sulfur atom or a nitrogen atom. Depending on the mode of bindingto the metal M, A can have a substituent group R⁶.

In formulae (XXII), (XXIII), (XXIV) and (XXV), D represents —C(R⁷)(R⁸)—,—Si(R⁹)(R¹⁰)—, —CO—, —SO₂—, —SO— or —P(O)(OR¹¹)—.

In formulae (XXII), (XXIII), (XXIV) and (XXV), m is an integer of 1 to6, preferably an integer of 1 to 4, more preferably an integer of 1 to3, still more preferably an integer of 1 to 2.

In formulae (XXII), (XXIII), (XXIV) and (XXV), R¹ to R¹¹ may be the sameor different and each represent a hydrogen atom, a halogen atom, ahydrocarbon group, an oxygen-containing group, a nitrogen-containinggroup, a boron-containing group, a sulfur-containing group, aphosphorus-containing group, a heterocyclic compound residue, asilicon-containing group, a germanium-containing group or atin-containing group, and two or more of these groups may be bound toeach other to form a ring. When m is 2 or more, R¹s, R²s, R³s, R⁴s, R⁵s,R⁶s, R⁷s, R⁸s, R⁹s, R¹⁰s or R¹¹s may be the same or different, and atleast one of groups represented by R¹ to R¹¹ contained in one ligand maybe bound to at least one of groups represented by R¹ to R¹¹ contained inanother ligand.

The halogen atom, hydrocarbon group, oxygen-containing group,nitrogen-containing group, boron-containing group, sulfur-containinggroup, phosphorus-containing group, heterocyclic compound residue,silicon-containing group, germanium-containing group and tin-containinggroup represented by R¹ to R¹¹ in formulae (XXII), (XXIII), (XXIV) and(XXV) include, for example, the same atom or group illustrated as R¹ toR⁷ in the general formula (I) above.

In formulae (XXII), (XXIII), (XXIV) and (XXV), n is a number satisfyingthe valence of M, and is specifically an integer of 1 to 5, preferably 1to 4, more preferably 1 to 3.

In formulae (XXII), (XXIII), (XXIV) and (XXV), X represents a hydrogenatom, a halogen atom, an oxygen atom, a hydrocarbon group, anoxygen-containing group, a sulfur-containing group, anitrogen-containing group, a boron-containing group, analuminum-containing group, a phosphorus-containing group, ahalogen-containing group, a heterocyclic compound residue, asilicon-containing group, a germanium-containing group or atin-containing group, and when n is 2 or more, a plurality of groupsrepresented by Xs may be the same or different, and a plurality ofgroups represented by Xs may be bound to each other to form a ring.

The halogen atom, hydrocarbon group, oxygen-containing group,sulfur-containing group, nitrogen-containing group, boron-containinggroup, aluminum-containing group, phosphorus-containing group,halogen-containing group, heterocyclic compound residue,silicon-containing group, germanium-containing group and tin-containinggroup represented by X in formulae (XXII), (XXIII), (XXIV) and (XXV)include, for example, the same atom or group illustrated as X¹ in thegeneral formula (I) above.

Compound (a-24)

As the component (A) in the present invention, compound (a-24)represented by the following general formula (XXVI), (XXVII), (XXVIII)or (XXVIX) can be used.

In formulae (XXVI), (XXVII), (XXVIII) and (XXVIX), M represents atransition metal atom selected from the groups 3 to 11 in the periodictable, preferably a transition metal atom in the groups 3 to 6 and 8 to10, more preferably a transition metal atom in the group 4, 5 or 6,still more preferably a metal atom in the group 4 or 5.

In formulae (XXVI), (XXVII), (XXVIII) and (XXVIX), m is an integer of 1to 6, preferably an integer of 1 to 4, more preferably an integer of 1to 3, still more preferably an integer of 1 to 2.

In formulae (XXVI), (XXVII), (XXVIII) and (XXVIX), A represents anoxygen atom, a sulfur atom or a nitrogen atom. Depending on the mode ofbinding to the metal M, A can have a substituent group R⁵.

In formulae (XXVI), (XXVII), (XXVIII) and (XXVIX), B representsN-binding groups —R⁶ and —R⁷, ═NR⁸ or ═CR⁹R¹⁰.

In formulae (XXVI), (XXVII), (XXVIII) and (XXVIX), R¹ to R¹⁰ may be thesame or different and each represent a hydrogen atom, a halogen atom, ahydrocarbon group, an oxygen-containing group, a nitrogen-containinggroup, a boron-containing group, a sulfur-containing group, aphosphorus-containing group, a heterocyclic compound residue, asilicon-containing group, a germanium-containing group or atin-containing group, and two or more of these groups may be bound toeach other to form a ring. When m is 2 or more, two groups out of thegroups represented by R¹ to R¹⁰ may be bound to one another to form aring, and Rs may be the same or different.

The halogen atom, hydrocarbon group, oxygen-containing group,nitrogen-containing group, boron-containing group, sulfur-containinggroup, phosphorus-containing group, heterocyclic compound residue,silicon-containing group, germanium-containing group and tin-containinggroup represented by R¹ to R¹⁰ in formulae (XXVI), (XXVII), (XXVIII) and(XXVIX) include, for example, the same atom or group illustrated as R¹to R⁷ in the general formula (I) above.

In formulae (XXVI), (XXVII), (XXVIII) and (XXVIX), n is a numbersatisfying the valence of M, and is specifically an integer of 1 to 5,preferably 1 to 4, more preferably 1 to 3.

In formulae (XXVI), (XXVII), (XXVIII) and (XXVIX), X represents ahydrogen atom, a halogen atom, an oxygen atom, a hydrocarbon group, anoxygen-containing group, a sulfur-containing group, anitrogen-containing group, a boron-containing group, analuminum-containing group, a phosphorus-containing group, ahalogen-containing group, a heterocyclic compound residue, asilicon-containing group, a germanium-containing group or atin-containing group, and when n is 2 or more, a plurality of groupsrepresented by Xs may be the same or different, and a plurality ofgroups represented by Xs may be bound to each other to form a ring.

The halogen atom, hydrocarbon group, oxygen-containing group,sulfur-containing group, nitrogen-containing group, boron-containinggroup, aluminum-containing group, phosphorus-containing group,halogen-containing group, heterocyclic compound residue,silicon-containing group, germanium-containing group and tin-containinggroup represented by X in formulae (XXVI), (XXVII), (XXVIII) and (XXVIX)include, for example, the same atom or group illustrated as X¹ in thegeneral formula (I) above.

Compound (a-25)

As the component (A) in the present invention, compound (a-25)represented by the following general formula (XXX) can be used.

In formula (XXX), M represents a transition metal atom selected from thegroups 3 to 11 in the periodic table, preferably a transition metal atomin the groups 3 to 6 and 8 to 10, more preferably a transition metalatom in the group 4, 5 or 6, still more preferably a metal atom in thegroup 4 or 5.

In formula (XXX), A¹ and A² may be the same or different and eachrepresent a nitrogen atom or a phosphorus atom.

In formula (XXX), Q¹ to Q⁶ may be the same or different and eachrepresent a nitrogen atom, a phosphorus atom, or a substituent—R²-containing carbon atom (—C(R²)═), and when a plurality of sustituent—R²-containing carbon atoms are present in Q¹ to Q⁶, the R²s may be thesame or different.

In formula (XXX), R¹ and R² may be the same or different and eachrepresent a hydrogen atom, a halogen atom, a hydrocarbon group, aheterocyclic compound residue, an oxygen-containing group, anitrogen-containing group, a boron-containing group, a sulfur-containinggroup, a phosphorus-containing group, a silicon-containing group, agermanium-containing group or a tin-containing group, and two or more ofthese groups may be bound to each other to form a ring.

The halogen atom, hydrocarbon group, oxygen-containing group,nitrogen-containing group, boron-containing group, sulfur-containinggroup, phosphorus-containing group, heterocyclic compound residue,silicon-containing group, germanium-containing group and tin-containinggroup represented by R¹ and R² in formula (XXX) include, for example,the same atom or group illustrated as R¹ to R⁷ in the general formula(I) above.

In formula (XXX), m is an integer of 1 to 6, preferably an integer of 1to 4, more preferably an integer of 1 to 3, still more preferably aninteger of 1 to 2. When m is 2 or more, R¹ or R¹¹ contained in oneligand may be bound to R¹ or R¹¹ contained in another ligand, and R¹s orR²s may be the same or different.

In formula (XXX), n is a number satisfying the valence of M, and isspecifically an integer of 1 to 5, preferably 1 to 4, more preferably 1to 3.

In formula (XXX), X represents a hydrogen atom, a halogen atom, anoxygen atom, a hydrocarbon group, an oxygen-containing group, asulfur-containing group, a nitrogen-containing group, a boron-containinggroup, an aluminum-containing group, a phosphorus-containing group, ahalogen-containing group, a heterocyclic compound residue, asilicon-containing group, a germanium-containing group or atin-containing group, and when n is 2 or more, a plurality of groupsrepresented by Xs may be the same or different, and a plurality ofgroups represented by Xs may be bound to each other to form a ring.

The halogen atom, hydrocarbon group, oxygen-containing group,sulfur-containing group, nitrogen-containing group, boron-containinggroup, aluminum-containing group, phosphorus-containing group,halogen-containing group, heterocyclic compound residue,silicon-containing group, germanium-containing group and tin-containinggroup represented by X in formula (XXX) include, for example, the sameatom or group illustrated as X¹ in the general formula (I) above.

Compound (a-26)

As the component (A) in the present invention, compound (a-26)represented by the following general formula (XXXIa) or (XXXIIa) can beused.

In formulae (XXXIa) and (XXXIIa), M represents a transition metal atomselected from the groups 3 to 6 in the periodic table, preferably atransition metal atom in the groups 4 and 5.

In formulae (XXXIa) and (XXXIIa), R¹ to R⁶ may be the same or differentand each represent a hydrogen atom, a hydrocarbon group, a C₁₋₂₀halogenated hydrocarbon group, an oxygen-containing group, asulfur-containing group, a silicon-containing group, anitrogen-containing group or a phosphorus-containing group, and two ormore of these groups may be bound to each other to form a ring.

The hydrocarbon group, C₁₋₂₀ halogenated hydrocarbon group,oxygen-containing group, sulfur-containing group, silicon-containinggroup, nitrogen-containing group and phosphorus-containing grouprepresented by R¹ to R⁶ in formulae (XXXIa) and (XXXIIa) include, forexample, the hydrocarbon group, halogenated hydrocarbon group,oxygen-containing group, sulfur-containing group, silicon-containinggroup, nitrogen-containing group and phosphorus-containing groupillustrated as R¹ to R⁷ in the general formula (I) above.

In formulae (XXXIa) and (XXXIIa), n is a number satisfying the valenceof M, and is specifically an integer of 1 to 5, preferably 1 to 4, morepreferably 1 to 3.

In formulae (XXXIa) and (XXXIIa), Xs may be the same or different andeach represent a hydrogen atom, a halogen atom, an oxygen atom, a C₁₋₂₀hydrocarbon group, a C₁₋₂₀ halogenated hydrocarbon group, anoxygen-containing group or a sulfur-containing group.

The halogen atom, C₁₋₂₀ hydrocarbon group, C₁₋₂₀ halogenated hydrocarbongroup, oxygen-containing group and sulfur-containing group representedby X in formulae (XXXIa) and (XXXIIa) include, for example, the halogenatom, hydrocarbon group, halogenated hydrocarbon group,oxygen-containing group and sulfur-containing group illustrated as R¹ toR⁷ in the general formula (I) above.

Compound (a-27)

As the component (A) in the present invention, compound (a-27)represented by the following general formula (XXXIb) or (XXXIIb) can beused.

In formulae (XXXIb) and (XXXIIb), M represents a transition metal atomselected from the groups 8 to 11 in the periodic table, preferably atransition metal atom selected from the groups 8 and 9.

In formulae (XXXIb) and (XXXIIb), R¹ to R⁶ may be the same or differentand each represent a hydrogen atom, a hydrocarbon group, a C₁₋₂₀halogenated hydrocarbon group, an oxygen-containing group, asulfur-containing group, a silicon-containing group, anitrogen-containing group or a phosphorus-containing group, and two ormore of these groups may be bound to each other to form a ring.

The hydrocarbon group, C₁₋₂₀ halogenated hydrocarbon group,oxygen-containing group, sulfur-containing group, silicon-containinggroup, nitrogen-containing group and phosphorus-containing grouprepresented by R¹ to R⁶ in formulae (XXXIb) and (XXXIIb) include, forexample, the hydrocarbon group, halogenated hydrocarbon group,oxygen-containing group, sulfur-containing group, silicon-containinggroup, nitrogen-containing group and phosphorus-containing groupillustrated as R¹ to R⁷ in the general formula (I) above.

In formulae (XXXIb) and (XXXIIb), n is a number satisfying the valenceof M, and is specifically an integer of 1 to 5, preferably 1 to 4, morepreferably 1 to 3.

In formulae (XXXIb) and (XXXIIb), Xs may be the same or different andeach represent a hydrogen atom, a halogen atom, an oxygen atom, a C₁₋₂₀hydrocarbon group, a C₁₋₂₀ halogenated hydrocarbon group, anoxygen-containing group or a sulfur-containing group.

The halogen atom, C₁₋₂₀ hydrocarbon group, C₁₋₂₀ halogenated hydrocarbongroup, oxygen-containing group and sulfur-containing group representedby X in formula (XXXIb) and (XXXIIb) include, for example, the halogenatom, hydrocarbon group, halogenated hydrocarbon group,oxygen-containing group and sulfur-containing group illustrated as R¹ toR⁷ in the general formula (I) above.

In the present invention, the transition metal compound (A) in thegroups 3 to 11, having a ligand containing two or more atoms selectedfrom a boron atom, a nitrogen atom, an oxygen atom and a sulfur atom maybe carried on the carrier component (B). The transition metal compound(A) is carried the carrier component (B) by mixing the transition metalcompound (A) with the carrier component (B) under stirring in an inertsolvent for a predetermined time and then collecting the mixture byfiltration, during which a heating procedure may be carried out. Theinert solvent includes aromatic hydrocarbons such as benzene, tolueneand xylene, aliphatic saturated hydrocarbons such as hexane, heptane anddecane, alicyclic hydrocarbons such as cyclohexane andmethylcyclopentane, and halogenated hydrocarbons such as ethylenechloride, chlorobenzene and dichloromethane, or mixtures thereof. Inheating, the temperature is varied depending on the solvent used, but isusually from a temperature higher the solidification point of thesolvent to 200° C., preferably up to 150° C. The stirring mixing time isvaried depending on temperature, but is usually 30 seconds to 24 hours,preferably 10 minutes to 10 hours. A filtration method used in usualorganic synthesis chemistry can be used in collection by filtration. Acake component after collection by filtration may be washed as necessarywith the above-mentioned aromatic hydrocarbon or aliphatic hydrocarbon.The carrier thus obtained also satisfies a feature of the carriercomponent of the present invention, that is, the molar ratio ofmagnesium atom to aluminum atom (Mg/Al) in the range of 1<Mg/Al≦300.0and the molar ratio of alkoxy group to aluminum atom (OR/Al) in therange of 0.05<OR/Al<2.0.

As the specific organometallic compound (C) (also referred tohereinafter as “organometallic compound”) used if necessary in thepresent invention, the following organometallic compounds in the groups1 and 2 and groups 12 and 13 in the periodic table can be arbitrarilyused.

Organoaluminum compounds represented by:The general formula: R^(a) _(m)Al(OR^(b))_(n)H_(p)X_(q)  (C-1a)wherein R^(a) and R^(b) may be the same or different and each representa C₁₋₂₀, preferably C₁₋₁₀, more preferably C₁₋₈, hydrocarbon group, Xrepresents a halogen atom, m is a number of 0<m≦3, n is a number of0≦n<3, p is a number of 0≦p<3, and q is a number of 0≦q<3, andsimultaneously m+n+p+q=3. Examples of such compounds include trimethylaluminum, triethyl aluminum, triisobutyl aluminum, trioctyl aluminum,and diisobutyl aluminum hydride.

Group 1 metal in the periodic table/aluminum alkylated complexesrepresented by:The general formula: M^(a)AlR^(a) ₄  (C-1b)wherein M^(a) represents Li, Na or K, and R^(a) represents a C₁₋₁₅,preferably C₁₋₄, hydrocarbon group. Examples of such compounds includeLiAl(C₂H₅) 4, LiAl(C₇H₁₅)₄ etc.

Dialkyl compounds of the group 2 or 12 metal in the periodic tablerepresented by:The general formula: R^(a)R^(b)M^(b)  (C-1c)wherein R^(a) and R^(b) may be the same or different and each representa C₁₋₁₅, preferably C₁₋₄, hydrocarbon group, and M^(b) is Mg, Zn or Cd.Among the specific organometallic compounds (C) described above, theorganoaluminum compound is preferable, and especially the aluminumcompound (C-1a) is preferable. The organometallic compounds (C-1) may beused alone or as a mixture of two or more thereof.

One feature of the present invention lies in that a conventionally usedorganoaluminum oxy compound or organoboron compound is not used incombination with a transition metal compound by using the carriercomponent of the present invention. Accordingly, at least one compoundselected from (C-1a), (C-1b) and (C-1c) is satisfactory as an arbitrarycomponent in the olefin polymerization catalyst, but the followingorganometallic compounds (C-2) and (C-3) may be contained as theorganometallic compound (C) in the olefin polymerization catalyst of thepresent invention to further improve the olefin polymerization activity.

(C-2) Organoaluminum Oxy Compound

The organoaluminum oxy compound (C-2) used in the present invention maybe aluminoxane known in the art or may be a benzene-insolubleorganoaluminum oxy compound illustrated in JP-A 2-78687.

The aluminoxane known in the art can be produced for example by thefollowing methods, and is obtained usually as a solution in ahydrocarbon solvent.

(1) A method in which an organoaluminum compound such as trialkylaluminum is added to a hydrocarbon suspension of a compound containingadsorbed water or a salt containing water of crystallization, forexample magnesium chloride hydrate, copper sulfate hydrate, aluminumsulfate hydrate, nickel sulfate hydrate or cerous chloride hydrate, andthe adsorbed water or water of crystallization is reacted with theorganoaluminum compound.

(2) A method in which water, ice or water vapor is allowed to actdirectly on an organoaluminum compound such as trialkyl aluminum in amedium such as benzene, toluene, ethyl ether or tetrahydrofuran.

(3) A method in which an organotin oxide such as dimethyltin oxide, ordibutyltin oxide is reacted with an organoaluminum compound such astrialkyl aluminum in a medium such as decane, benzene or toluene.

The aluminoxane may contain a small amount of an organic metalcomponent. From the recovered solution of aluminoxane, a solvent orunreacted organoaluminum compound is removed by distillation, and thealuminoxane may be re-dissolved in a solvent or suspended in a poorsolvent for aluminoxane.

The examples of organoaluminum compound used in preparing thealuminoxane includes the same organoaluminum compound as illustrated forthe organoaluminum compound belonging to the above-mentioned (B-1a).

Among these, trialkyl aluminum and tricycloalkyl aluminum arepreferable, and trimethyl aluminum is particularly preferable.

The organoaluminum compounds described above are used alone or as amixture of two or more thereof.

The benzene-insoluble organoaluminum oxy compound used in the presentinvention is preferably insoluble or sparingly soluble in benzenewherein the Al component dissolved in benzene at 60° C. is usually 10%or less, preferably 5% or less, particularly preferably 2% or less, interms of Al atom. These organoaluminum oxy compounds (B-2) are usedalone or as a mixture of two or more thereof.

(C-3) Compound which Reacts with a Transition Metal Compound to Form anIon Pair

Compound (C-3) which reacts with the transition metal compound (A) inthe present invention to form an ion pair (hereinafter referred to as“ionized ionic compound”) includes Lewis acid, ionic compounds, boranecompounds and carborane compounds described in JP-A 1-501950, JP-A1-502036, JP-A 3-179005, JP-A 3-179006, JP-A 3-207703, JP-A 3-207704 andU.S. Pat. No. 5,321,106. Further, heteropoly compounds and isopolycompounds can also be mentioned. These ionized ionic compounds (C-3) canbe used alone or as a mixture of two or more thereof.

In the olefin polymerization catalyst of the present invention,inorganic carriers of SiO₂, Al₂O₃, MgO, ZrO, TiO₂, B₂O₃, CaO, ZnO, BaOand ThO₂ or organic carriers of granular or fine particle organicpolymers having a particle diameter of 10 to 300 μm such aspolyethylene, polypropylene, polybutene and polystyrene can be used inaddition to the carrier component (B), the transition metal compound (A)and the specific organometallic compound (C).

Method of Polymerizing an Olefin, and Polyolefin Obtained by this Method

The polyolefin of the present invention is a polyolefin having a bulkdensity of 0.20 (g/cm³) or more, which obtained in the presence of theolefin polymerization catalyst by homopolymerizing or copolymerizingolefins by the high activity of the catalyst.

The olefin subjected to the polymerization reaction in the presentinvention is at least one monomer selected from ethylene and α-olefin,and at least one monomer is ethylene or propylene. The α-olefin includesC₃₋₂₀, preferably C₃₋₁₀, linear or branched α-olefins, for example,propylene, 1-butene, 2-butene, 1-pentene, 3-methyl-1-butene, 1-hexene,4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene,1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicocene. In thepolymerization method of the present invention, mention can be made ofC₃₋₃₀, preferably C₃₋₂₀, cyclic olefins, for example cyclopentene,cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene,2-methyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene; polarmonomers, for example allyl alcohol and α,β-unsaturated carboxylic acidssuch as acrylic acid, methacrylic acid, fumaric acid, maleic anhydride,itaconic acid, itaconic anhydride,bicyclo(2,2,1)-5-heptene-2,3-dicarboxylic anhydride, and metal saltsthereof such as sodium salt, potassium salt, lithium salt, zinc salt,magnesium salt, calcium salt etc.; α,β-unsaturated carboxylates such asmethyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate,n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-ethylhexylacrylate, methyl methacrylate, ethyl methacrylate, n-propylmethacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutylmethacrylate etc.; vinyl esters such as vinyl acetate, vinyl propionate,vinyl caproate, vinyl caprinate, vinyl laurate, vinyl stearate, vinyltrifluoroacetate etc.; and unsaturated glycidyl such as glycidylacrylate, glycidyl methacrylate, monoglycidyl itaconate etc. Further,vinyl cyclohexane, diene or polyene; an aromatic vinyl compound, forexample mono- or polyalkyl styrene such as styrene, o-methyl styrene,m-methyl styrene, p-methyl styrene, o,p-dimethyl styrene, o-ethylstyrene, m-ethyl styrene, p-ethyl styrene etc.; a functionalgroup-containing styrene derivative such as methoxy styrene, ethoxystyrene, vinylbenzoic acid, methyl vinylbenzoate, vinylbenzyl acetate,hydroxy styrene, o-chlorostyrene, p-chlorostyrene, divinyl benzene etc.;and 3-phenylpropylene, 4-phenylpropylene, α-methylstyrene can be allowedto be present in the reaction system to allow the polymerization toproceed.

In the method of polymerizing olefins according to the presentinvention, olefins are polymerized or copolymerized in the presence ofthe olefin polymerization catalyst described above, to give an olefinpolymer.

The polymerization in the present invention can be carried out byliquid-phase polymerization such as solution polymerization orsuspension polymerization or by gaseous-phase polymerization. Examplesof inert hydrocarbon solvents used in solution polymerization orsuspension polymerization include aliphatic hydrocarbons such aspropane, butane, pentane, hexane, heptane, octane, decane, dodecane andkerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane andmethylcyclopentane; aromatic hydrocarbons such as benzene, toluene andxylene; halogenated hydrocarbons such as ethylene chloride,chlorobenzene and dichloromethane, or mixtures thereof, and olefinsthemselves can also be used as the solvent.

When the olefin polymerization catalyst described above is used inpolymerization of olefins, the component (A) is used usually in anamount of 10⁻⁸ to 10⁻² mole, preferably 10⁻⁷ to 10⁻³ mole, per L of thereaction volume.

Component (B) is used in such an amount that the molar ratio of themagnesium atom to the total transition metal atom (M) in component (B)[Mg/M] is usually 1.0 to 1000, preferably 10 to 800. Component (C) isused in such an amount that the molar ratio of the metal atom (M′) incomponent (C) to the total transition metal atom (M) in component (A)[M′/M] is usually 5 to 5000, preferably 100 to 3000.

The temperature of polymerization of an olefin by using the olefinpolymerization catalyst is usually in the range of −50 to +200° C.,preferably o to 170° C. The polymerization pressure is usually normalpressures to 10 MPa gauge pressure, preferably normal pressures to 5 MPagauge pressure, and the polymerization reaction can be carried out in abatch, semi-continuous or continuous system. Further, polymerization canbe carried out in two or more stages different in reaction conditions.The molecular weight of the obtained olefin polymer can be regulated byallowing hydrogen, an organosilane compound or another knownmolecular-weight regulator to be present in the polymerization system orby changing the polymerization temperature. Further, the molecularweight can be regulated by changing the amount of component (A) used.

The polymer obtained by the polymerization method of the presentinvention described above is characterized in that its bulk density is0.20 (g/cm³) or more, preferably 0.22 (g/cm³) or more. In addition, thepolymer is characterized in that the molecular-weight distribution(Mw/Mn) determined by GPC can be changed not only by a polymerizationprocess such as multi-stage polymerization, but can also be regulated byselection of component (A) and can be changed in the Mw/Mn range of 1 to150, and the polymer can be produced so as to adaptable for varioususes.

Now, a major analytical method in the present invention, and methods ofmeasuring the physical properties and properties of polymers obtained bypolymerization of olefins are described.

[Analysis of the Composition of the Carrier Component]

The metal content in the carrier component was determined by plasmaemission mass spectrometry. The halogen content was determined bypotential difference titration, and the alkoxy group content by gaschromatography.

[Average Particle Diameter of the Carrier Component]

The number-average particle diameter was determined by an opticaltransmission sedimentation method using a known Stokes formula (Equation1). The unit used was an automatic particle-size distribution measuringunit (CAPA-300, manufactured by HORIBA, Ltd.). The dispersant used was amixed solution of decalin and triolein (decalin/triolein=1/4 (weightratio)).$D = \left( \frac{18\quad\eta_{0}{\ln\left( {X_{2}/X_{1}} \right)}}{\left( {\rho - \rho_{0}} \right)\omega^{2}t} \right)^{1/2}$D: Particle diameter of catalyst (cm)η₀: Viscosity coefficient of dispersant (poise)ρ: Sample density (g/cm³)ρ₀: Dispersant density (g/cm³)t: Sedimentation time (sec.)X₁: Distance from rotation center to sedimentation surface (cm)X₂: Distance from rotation center to measurement surface (cm)ω: Rotation angular velocity (rad/sec.)[Crystallite Size of the Carrier Component]

The crystallite size was determined by measuring the half band widthvalue of a magnesium chloride (110) face with an X-ray diffraction unit(RU-300 manufactured by Rigaku Corporation.) and by applying a knownScherrer's equation (in the equation, 0.9 is attributable to theconstant K). All samples used in measuring their crystallite size werehandled in a nitrogen atmosphere. The method of measuring thecrystallite size by using the Scherrer formula is described in detail inEssence of Cullity X-Ray Diffraction (in Japanese) (translated byGentaro Matsumura) published by Agne Co., Ltd.

[Weight-Average Molecular Weight (Mw) and Number-Average MolecularWeight (Mn) of the Polymer]

Calculated from a molecular-weight distribution curve obtained by Watersmodel [Alliance GPC 2000] gel permeation chromatography(high-temperature size-extrusion chromatography). The operationconditions are as follows:

Mobile phase: o-Dichlorobenzene (Wako Pure Chemical Industries, Ltd.)

Flow rate of mobile phase: 1 ml/min.

Columns: Two columns of TSK-GEL (registered trademark) model

GMH6-HT and two columns of TSK-GEL (registered trademark) modelGMH6-HTL.

Temperature: 140° C.

Sample concentration: 30 mg/20 ml (0.15% (w/v))

Injection volume: 500 μL

Detection method: Detection by a reflectometer integrated in achromatographic unit

[Intrinsic Viscosity [η] of the Polymer]

The intrinsic viscosity is a value measured at 135° C. in a decalinsolvent. That is, about 20 g granulated pellets are dissolved in 15 mldecal in and measured for its specific viscosity η_(sp) in an oil bathat 135° C. This decalin solution is diluted with additional 5 ml decalinsolvent, and then measured for its specific viscosity η_(sp) in the samemanner as above. This diluting procedure is repeated further twice, andthe value of η_(sp)/C upon extrapolation of concentration (C) to 0 isdetermined as the intrinsic viscosity.

[η]=lim(η_(sp)/C) (C→0)

[Melt flow rate (MFR_(2.16))]

A value determined at 190° C. under a loading of 2.16 kg by a standardmethod of ASTM D-1238.

[Polymer Bulk Density]

Determined from the weight of a sample in a container having an internalvolume of 100 ml according to JIS K-6721.

EXAMPLES

Hereinafter, the present invention is described in more detail byreference to the Examples, but the present invention is not limited tothe Examples. The structures of compounds obtained in the synthesisexamples were determined by using 270 MHz ¹H-NMR (JEOL GSH-270), FD-massspectrometry (JEOL SX-102A) etc.

Example 1

Preparation of Component (b1)

95.2 g (1.0 mole) anhydrous magnesium chloride, 442 ml decane and 390.6g (3.0 moles) 2-ethylhexyl alcohol were reacted at 130° C. for 2 hoursto give a uniform solution (component (b1)).

Preparation of Component (b1-1)

A flask having an internal volume of 200 ml purged sufficiently withnitrogen was charged with 25 ml component (b1) (25 mmol in terms ofmagnesium atom) and 100 ml purified decane, and while the temperature ofthe solution was kept at 15° C. under stirring, 26 mmol triethylaluminum diluted with purified decane was added dropwise thereto over 30minutes. Thereafter, the temperature of the solution was increased to80° C. over 120 minutes, and the mixture was reacted for additional 60minutes. While the temperature was kept at 80° C., 49 mmol triethylaluminum diluted with purified decane was again added dropwise theretoover 30 minutes, and the mixture was further reacted under heating for60 minutes. After the reaction was finished, the solids were collected yfiltration and washed sufficiently with toluene, and 100 ml toluene wasadded thereto to form a toluene slurry of component (b1-1). The averageparticle diameter of the resulting component (b1-1) was 20 μm.

A part of the component (b1-1) prepared by the above procedure was driedand examined for its composition, indicating 17.0 weight % magnesium,2.9 weight % aluminum, 26.4 weight % 2-ethylhexoxy group and 49.0 weight% chlorine. Accordingly, the molar ratio of magnesium to aluminum(Mg/Al) was 6.5, and the molar ratio of 2-ethylhexoxy group to aluminum(OR/Al) was 1.9.

Preparation of Component (b1-1-a2-172)

A flask having an internal volume of 200 ml purged sufficiently withnitrogen was charged with purified toluene so as to adjust the totalvolume to 154.1 ml and with component (b1-1) in an amount of 10 mmol interm of magnesium atom. While the sample was kept at 25° C. understirring, 45.9 ml toluene solution (0.001089 mmol/ml) of component(a2-172) below was added dropwise thereto over 20 minutes. After themixture was stirred for 1 hour, the solids were collected by filtrationand washed sufficiently with toluene, and 100 ml purified decane wasadded thereto to give a decane slurry of component (b1-1-a2-172).

A part of this slurry was collected to analyze its concentration,indicating 1.30 mg/mL magnesium and 20.8 μg/mL zirconium. Accordingly,the content of zirconium atom in 1 g of the component (b1-1-a2-172) wascalculated to be 2.7 mg/g.

From the ICP-MASS spectrometry of a dry sample of the component(b1-1-a2-172), it was confirmed that 0.28 weight % zirconium atom wascontained. The other components were 17.0 weight % magnesium, 2.8 weight% aluminum, 25.1 weight % 2-ethylhexyl group, and 51.0 weight %chlorine. Accordingly, the molar ratio of magnesium to aluminum (Mg/Al)was 6.7, and the molar ratio of 2-ethylhexoxy group to aluminum (OR/Al)was 1.9, and it was confirmed that the molar ratio was hardly changedfrom the corresponding molar ratio of component (b1-1).

Polymerization

500 ml purified heptane was introduced into an SUS autoclave having aninternal volume of 1 liter purged sufficiently with nitrogen, and theliquid phase and gaseous phase were saturated with ethylene by blowingethylene. Thereafter, the heptane was heated to 75° C., and theautoclave was charged in an ethylene atmosphere with 0.5 mmol triethylaluminum and the above component (b1-1-a2-172) (0.0004 mmol in terms ofzirconium atom) in this order. Polymerization was carried out for 60minutes at an ethylene pressure of 0.8 MPa-G. During the polymerization,the system was kept at 80° C. and at an ethylene pressure of 0.8 MPa·G.After the polymerization was finished, the reaction product was washedwith a large amount of hexane and collected by filtration with a glassfilter. The resulting polymer was dried under vacuum for 10 hours togive 66.9 g polyethylene.

The polymerization activity was 167.2 kg/mmol-Zr·hr, and thepolymerization activity per g of the component (b1-1-a2-172) was 5.1kg/g-cat-hr, and this polyethylene had a [η] value of 16.3 dl/g and abulk density of 0.24 g/cm³. The Mw of this polyethylene as determined byGPC was 1.9×10⁶, and the Mw/Mn ratio was 4.1.

Example 2

Preparation of Component (b1-1-a2-140)

A flask having an internal volume of 200 ml purged sufficiently withnitrogen was charged with purified toluene so as to adjust the totalvolume to 128.4 ml and with component (b1-1) in an amount of 10 mmol interm of magnesium atom. While the sample was kept at 25° C. understirring, 71.6 ml toluene solution (0.000699 mmol/ml) of component(a2-140) below was added dropwise thereto over 20 minutes. After themixture was stirred for 1 hour, the solids were collected by filtrationand washed sufficiently with toluene, and 100 ml purified decane wasadded thereto to give a decane slurry of component (b1-1-a2-140).

A part of the component (b1-1-a2-140) prepared by the above procedurewas dried and examined for its composition, indicating 16.0 weight %magnesium, 2.7 weight % aluminum, 24.0 weight % 2-ethylhexoxy group,48.0 weight % chlorine and 0.30 weight % zirconium. Similarly to Example1, the analytical content of zirconium agreed well with the theoreticalcontent. The molar ratio of magnesium to aluminum (Mg/Al) was 6.3, andthe molar ratio of 2-ethylhexoxy group to aluminum (OR/Al) was 1.8, andit was confirmed that similarly to Example 1, the molar ratio hardlychanged from the corresponding molar ratio of the component (b1-1).

Polymerization

Polymerization was carried out in the same manner as in Example 1 exceptthat in the Polymerization in Example 1, the component (b1-1-a2-140)prepared above was used in place of the component (b1-1-a2-172). As aresult, 50.9 g polyethylene was obtained.

The polymerization activity was 127.3 kg/mmol-Zr·hr, and thepolymerization activity per g of the component (b1-1-a2-140) was 4.2kg/g-cat-hr, and this polyethylene had a [η]value of 18.3 dl/g and abulk density of 0.33 g/cm³. The Mw of this polyethylene as determined byGPC was 2.4×10⁶, and the Mw/Mn ratio was 5.9.

Example 3

Preparation of Component (b1-1-a2-204)

A flask having an internal volume of 200 ml purged sufficiently withnitrogen was charged with purified toluene so as to adjust the totalvolume to 125.5 ml and with component (b1-1) in an amount of 10 mmol interm of magnesium atom. While the sample was kept at 25° C. understirring, 74.5 ml toluene solution (0.000671 mmol/ml) of component(a2-204) below was added dropwise thereto over 20 minutes. After themixture was stirred for 1 hour, the solids were collected by filtrationand washed sufficiently with toluene, and 100 ml purified decane wasadded thereto to give a decane slurry of component (b1-1-a2-204).

Apart of the component (b1-1-a2-204) prepared by the above procedure wasdried and examined for its composition, indicating 17.0 weight %magnesium, 2.7 weight % aluminum, 24.0 weight % 2-ethylhexoxy group,50.0 weight % chlorine and 0.31 weight % zirconium. Accordingly, themolar ratio of magnesium to aluminum (Mg/Al) was 7.0, and the molarratio of 2-ethylhexoxy group to aluminum (OR/Al) was 1.8.

Polymerization

Polymerization was carried out in the same manner as in Example 1 exceptthat in the Polymerization in Example 1, the component (b1-1-a2-204)prepared above was used in place of the component (b1-1-a2-172). As aresult, 40.3 g polyethylene was obtained.

The polymerization activity was 100.8 kg/mmol-Zr·hr, and thepolymerization activity per g of the component (b1-1-a2-204) was 3.4kg/g-cat·hr, and this polyethylene had a [α]value of 18.1 dl/g and abulk density of 0.28 g/cm³. The Mw of this polyethylene as determined byGPC was 2.2×10⁶, and the Mw/Mn ratio was 7.1.

Example 4

Preparation of Component (b1-1-a2-126)

A flask having an internal volume of 200 ml purged sufficiently withnitrogen was charged with purified toluene so as to adjust the totalvolume to 153.8 ml and with component (b1-1) in an amount of 10 mmol interm of magnesium atom. While the sample was kept at 25° C. understirring, 46.2 ml toluene solution (0.001083 mmol/ml) of component(a2-126) below was added dropwise thereto over 20 minutes. After themixture was stirred for 1 hour, the solids were collected by filtrationand washed sufficiently with toluene, and 100 ml purified decane wasadded thereto to give a decane slurry of component (b1-1-a2-126).

A part of the component (b1-1-a2-126) prepared by the above procedurewas dried and examined for its composition, indicating 17.0 weight %magnesium, 2.8 weight % aluminum, 25.8 weight % 2-ethylhexoxy group,51.0 weight % chlorine and 0.31 weight % zirconium. Accordingly, themolar ratio of magnesium to aluminum (Mg/Al) was 6.7, and the molarratio of 2-ethylhexoxy group to aluminum (OR/Al) was 1.9.

Polymerization

Polymerization was carried out in the same manner as in Example 1 exceptthat in the Polymerization in Example 1, the component (b1-1-a2-126)(0.001 mmol in terms of zirconium atom) prepared above was used in placeof the component (b1-1-a2-172) As a result, 20.5 g polyethylene wasobtained.

The polymerization activity was 20.5 kg/mmol-Zr·hr, and thepolymerization activity per g of the component (b1-1-a2-126) was 0.7kg/g-cat·hr, and this polyethylene had a [η] value of 0.5 dl/g and abulk density of 0.20 g/cm³. The Mw of this polyethylene as determined byGPC was 1.1×10⁴, and the Mw/Mn ratio was 3.0.

Example 5

Preparation of Component (b1-1-a2-116)

A flask having an internal volume of 200 ml purged sufficiently withnitrogen was charged with purified toluene so as to adjust the totalvolume to 131.8 ml and with component (b1-1) in an amount of 10 mmol interm of magnesium atom. While the sample was kept at 25° C. understirring, 68.2 ml toluene solution (0.000734 mmol/ml) of component(a2-116) below was added dropwise thereto over 20 minutes. After themixture was stirred for 1 hour, the solids were collected by filtrationand washed sufficiently with toluene, and 100 ml purified decane wasadded thereto to give a decane slurry of component (b1-1-a2-116).

A part of the component (b1-1-a2-116) prepared by the above procedurewas dried and examined for its composition, indicating 17.0 weight %magnesium, 2.8 weight % aluminum, 26.6 weight % 2-ethylhexoxy group,49.0 weight % chlorine and 0.30 weight % zirconium. Accordingly, themolar ratio of magnesium to aluminum (Mg/Al) was 6.7, and the molarratio of 2-ethylhexoxy group to aluminum (OR/Al) was 2.0.

Polymerization

Polymerization was carried out in the same manner as in Example 1 exceptthat in the Polymerization in Example 1, the component (b1-1-a2-116)(0.001 mmol in terms of zirconium atom) prepared above was used in placeof the component (b1-1-a2-172) As a result, 17.5 g polyethylene wasobtained.

The polymerization activity was 17.5 kg/mmol-Zr·hr, and thepolymerization activity per g of the component (b1-1-a2-116) was 0.6kg/g-cat·hr, and this polyethylene had a [η]value of 20.0 dl/g and abulk density of 0.31 g/cm³.

Example 6

Preparation of Component (b1-1-a2-228)

A flask having an internal volume of 200 ml purged sufficiently withnitrogen was charged with purified toluene so as to adjust the totalvolume to 150.0 ml and with component (b1-1) in an amount of 10 mmol interm of magnesium atom. While the sample was kept at 25° C. understirring, 50.0 ml toluene solution (0.00100 mmol/ml) of component(a2-228) below was added dropwise thereto over 20 minutes. After themixture was stirred for 1 hour, the solids were collected by filtrationand washed sufficiently with toluene, and 100 ml purified decane wasadded thereto to give a decane slurry of component (b1-1-a2-228).

Apart of the component (b1-1-a2-228) prepared by the above procedure wasdried and examined for its composition, indicating 18.0 weight %magnesium, 2.6 weight % aluminum, 20.0 weight % 2-ethylhexoxy group,54.0 weight % chlorine and 0.35 weight % zirconium. Accordingly, themolar ratio of magnesium to aluminum (Mg/Al) was 7.7, and the molarratio of 2-ethylhexoxy group to aluminum (OR/Al) was 1.6.

Polymerization

Polymerization was carried out in the same manner as in Example 1 exceptthat in the Polymerization in Example 1, the component (b1-1-a2-228)(0.001 mmol in terms of zirconium atom) prepared above was used in placeof the component (b1-1-a2-172) As a result, 8.8 g polyethylene wasobtained.

The polymerization activity was 8.8 kg/mmol-Zr·hr, and thepolymerization activity per g of the component (b1-1-a2-228) was 1.2kg/g-cat·hr, and the [α]value of this polyethylene was 0.24 dl/g. The Mwof this polyethylene as determined by GPC was 3.0×10³, and the Mw/Mnratio was 1.9.

Example 7

Preparation of Component (b1-1-a2-138)

A flask having an internal volume of 200 ml purged sufficiently withnitrogen was charged with purified toluene so as to adjust the totalvolume to 150.0 ml and with component (b1-1) in an amount of 10 mmol interm of magnesium atom. While the sample was kept at 25° C. understirring, 50.0 ml toluene solution (0.00100 mmol/ml) of component(a2-138) below was added dropwise thereto over 20 minutes. After themixture was stirred for 1 hour, the solids were collected by filtrationand washed sufficiently with toluene, and 100 ml purified decane wasadded thereto to give a decane slurry of component (b1-1-a2-138).

A part of the component (b1-1-a2-138) prepared by the above procedurewas dried and examined for its composition, indicating 18.0 weight %magnesium, 2.5 weight % aluminum, 20.5 weight % 2-ethylhexoxy group,51.0 weight % chlorine and 0.32 weight % zirconium. Accordingly, themolar ratio of magnesium to aluminum (Mg/Al) was 8.0, and the molarratio of 2-ethylhexoxy group to aluminum (OR/Al) was 1.7.

Polymerization

Polymerization was carried out in the same manner as in Example 1 exceptthat in the Polymerization in Example 1, the component (b1-1-a2-138)(0.001 mmol in terms of zirconium atom) prepared above was used in placeof the component (b1-1-a2-172) As a result, 55.5 g polyethylene wasobtained.

The polymerization activity was 55.5 kg/mmol-Zr·hr, and thepolymerization activity per g of the component (b1-1-a2-138) was 2.0kg/g-cat·hr, and this polyethylene had a [η] value of 13.7 dl/g and abulk density of 0.21 g/cm³. The Mw of this polyethylene as determined byGPC was 166.8×10⁴, and the Mw/Mn ratio was 12.3.

Example 8

Preparation of Component (b1-1-a2-241)

A flask having an internal volume of 200 ml purged sufficiently withnitrogen was charged with purified toluene so as to adjust the totalvolume to 150.0 ml and with component (b1-1) in an amount of 10 mmol interm of magnesium atom. While the sample was kept at 25° C. understirring, 50.0 ml toluene solution (0.00100 mmol/ml) of component(a2-241) below was added dropwise thereto over 20 minutes. After themixture was stirred for 1 hour, the solids were collected by filtrationand washed sufficiently with toluene, and 100 ml purified decane wasadded thereto to give a decane slurry of component (b1-1-a2-241).

Apart of the component (b1-1-a2-241) prepared by the above procedure wasdried and examined for its composition, indicating 18.0 weight %magnesium, 2.5 weight % aluminum, 22.8 weight % 2-ethylhexoxy group,52.0 weight % chlorine and 0.28 weight % zirconium. Accordingly, themolar ratio of magnesium to aluminum (Mg/Al) was 8.0, and the molarratio of 2-ethylhexoxy group to aluminum (OR/Al) was 1.9.

Polymerization

Polymerization was carried out in the same manner as in Example 1 exceptthat in the Polymerization in Example 1, the component (b1-1-a2-241)(0.001 mmol in terms of zirconium atom) prepared above was used in placeof the component (b1-1-a2-172) As a result, 22.6 g polyethylene wasobtained.

The polymerization activity was 22.6 kg/mmol-Zr·hr, and thepolymerization activity per g of the component (b1-1-a2-241) was 0.7kg/g-cat·hr, and this polyethylene had a [η]value of 9.7 dl/g and a bulkdensity of 0.20 g/cm³. The Mw of this polyethylene as determined by GPCwas 104.4×10⁴, and the Mw/Mn ratio was 23.8.

Example 9

Preparation of Component (b1-1-a2-134)

A flask having an internal volume of 200 ml purged sufficiently withnitrogen was charged with component (b1-1) in an amount of 4 mmol interm of magnesium atom and 100 ml purified toluene, and while the samplewas kept at room temperature under stirring, 18.8 ml toluene solution(0.00106 mmol/ml) of component (a2-172) below was added dropwise theretoover 20 minutes. After the mixture was stirred for 1 hour, the solidswere collected by filtration and washed sufficiently with toluene, and50 ml purified decane was added thereto to give a decane slurry ofcomponent (b1-1-a2-134).

A part of this slurry was collected to analyze its concentration,indicating 1.59 mg/mL magnesium and 30.0 μg/mL zirconium. Accordingly,the content of zirconium atom in 1 g of the component (b1-2-a2-134) wascalculated to be 3.2 mg/g.

Polymerization

Polymerization was carried out in the same manner as in Example 1 exceptthat in the Polymerization in Example 1, the component (b1-1-a2-134)(0.001 mmol in terms of zirconium atom) prepared above was used in placeof the component (b1-1-a2-172) As a result, 15.0 g polyethylene wasobtained.

The polymerization activity was 15.0 kg/mmol-Zr·hr, and thepolymerization activity per g of the component (b1-1-a2-241) was 0.5kg/g-cat·hr, and this polyethylene had a [η] value of 2.8 dl/g and abulk density of 0.23 g/cm³.

Example 10

Preparation of Component (b1-1-a2-195)

A flask having an internal volume of 200 ml purged sufficiently withnitrogen was charged with component (b1-1) in an amount of 4 mmol interm of magnesium atom and purified toluene so as to adjust the totalvolume to 85.4 ml, and while the sample was kept at room temperatureunder stirring, 14.6 ml toluene solution (0.00103 mmol/ml) of component(a2-195) below was added dropwise thereto over 20 minutes. After themixture was stirred for 1 hour, the solids were collected by filtrationand washed sufficiently with toluene, and 50 ml purified decane wasadded thereto to give a decane slurry of component (b1-1-a2-195).

A part of this slurry was collected to analyze its concentration,indicating 1.22 mg/mL magnesium and 21.2 μg/mL zirconium. Accordingly,the content of zirconium atom in 1 g of the component (b1-2-a2-195) wascalculated to be 3.0 mg/g.

Polymerization

500 ml purified heptane was introduced into an SUS autoclave having aninternal volume of 1 liter purged sufficiently with nitrogen, and theliquid phase and gaseous phase were saturated with ethylene by blowingethylene. Thereafter, the heptane was heated to 75° C., and theautoclave was charged in an ethylene atmosphere with 0.35 mmol triethylaluminum and the above component (b1-1-a2-195) (0.00035 mmol in terms ofzirconium atom) in this order. Polymerization was carried out for 60minutes at an ethylene pressure of 0.8 MPa·G. During the polymerization,the system was kept at 80° C. and at an ethylene pressure of 0.8 MPa-G.After the polymerization was finished, the reaction product was washedwith a large amount of hexane and collected by filtration with a glassfilter. The resulting polymer was dried under vacuum for 10 hours togive 41.2 g polyethylene.

The polymerization activity was 160.6 kg/mmol-Zr·hr, and thepolymerization activity per g of the component (b1-1-a2-195) was 3.9kg/g-cat·hr, and this polyethylene had a [η]value of 17.2 dl/g and abulk density of 0.28 g/cm³.

Example 11

Preparation of Component (b1-2)

A flask having an internal volume of 400 ml purged sufficiently withnitrogen was charged with 12.5 ml component (b1) (12.5 mmol in terms ofmagnesium atom) and 200 ml purified decane, and while the temperature ofthe solution was kept at 15° C. under stirring, 13 mmol triethylaluminum diluted with purified decane was added dropwise thereto over 30minutes. Thereafter, the temperature of the solution was increased to80° C. over 120 minutes, and the mixture was reacted for additional 60minutes. While the temperature was kept at 80° C., 24.5 mmol triethylaluminum diluted with purified decane was again added dropwise theretoover 30 minutes, and the mixture was further reacted under heating for60 minutes. After the reaction was finished, the solids were collectedby filtration and washed sufficiently with toluene, and 50 ml toluenewas added thereto to form a toluene slurry of component (b1-2). Theaverage particle diameter of the resulting component (b1-2) was 20 μm.

A part of the component (b1-2) prepared by the above procedure was driedand examined for its composition, indicating 18.0 weight % magnesium,26.0 weight % aluminum, 21.4 weight % 2-ethylhexoxy group and 52.0weight % chlorine. Accordingly, the molar ratio of magnesium to aluminum(Mg/Al) was 7.7, and the molar ratio of 2-ethylhexoxy group to aluminum(OR/Al) was 1.7.

Preparation of Component (b1-2-a2-172)

A flask having an internal volume of 200 ml purged sufficiently withnitrogen was charged with component (b1-1) in an amount of 3 mmol interm of magnesium atom and purified toluene so as to adjust the totalvolume to 85.1 ml, and while the sample was kept at room temperatureunder stirring, 14.9 ml toluene solution (0.001005 mmol/ml) of component(a2-195) below was added dropwise thereto over 20 minutes. After themixture was stirred for 1 hour, the solids were collected by filtrationand washed sufficiently with toluene, and 50 ml purified decane wasadded thereto to give a decane slurry of component (b1-1-a2-195).

A part of this slurry was collected to analyze its concentration,indicating 1.07 mg/mL magnesium and 26.5 μg/mL zirconium. Accordingly,the content of zirconium atom in 1 g of the component (b1-2-a2-172) wascalculated to be 4.5 mg/g.

Polymerization

Polymerization was carried out in the same manner as in Example 12except that in the Polymerization in Example 12, the component(b1-2-a2-172) prepared above was used in place of the component(b1-1-a2-195). As a result, 57.2 g polyethylene was obtained.

The polymerization activity was 163.3 kg/mmol-Zr·hr, and thepolymerization activity per g of the component (b2-1-a2-172) was 8.1kg/g-cat·hr, and this polyethylene had a [η] value of 17.4 dl/g and abulk density of 0.27 g/cm³.

Example 12

Preparation of Component (b2)

95.2 g (1.0 mole) anhydrous magnesium chloride, 551 ml decane and 325.5g (2.5 moles) 2-ethylhexyl alcohol were reacted at 130° C. for 2 hoursto give a uniform solution (component (b2))

Preparation of Component (b2-1)

A flask having an internal volume of 200 ml purged sufficiently withnitrogen was charged with 25 ml component (b2) (25 mmol in terms ofmagnesium atom) and 100 ml purified decane, and while the temperature ofthe solution was kept at 15° C. under stirring, 25 mmol triethylaluminum diluted with purified decane was added dropwise thereto over 30minutes. Thereafter, the temperature of the solution was increased to80° C. over 120 minutes, and the mixture was reacted for additional 60minutes. While the temperature was kept at 80° C., 37.5 mmol triethylaluminum diluted with purified decane was again added dropwise theretoover 30 minutes, and the mixture was further reacted under heating for60 minutes. After the reaction was finished, the solids were collectedby filtration and washed sufficiently with toluene, and 100 ml toluenewas added thereto to form a toluene slurry of component (b2-1) Theaverage particle diameter of the resulting component (b2-1) was 9 μm.

A part of the component (b2-1) prepared by the above procedure was driedand examined for its composition, indicating 18.0 weight % magnesium,2.3 weight % aluminum, 19.0 weight % 2-ethylhexoxy group and 54.0 weight% chlorine. Accordingly, the molar ratio of magnesium to aluminum(Mg/Al) was 8.7, and the molar ratio of 2-ethylhexoxy group to aluminum(OR/Al) was 1.6.

Preparation of Component (b2-1-a2-172)

A flask having an internal volume of 200 ml purged sufficiently withnitrogen was charged with component (b2-1) in an amount of 4 mmol interm of magnesium atom and purified toluene so as to adjust the totalvolume to 85.4 ml, and while the sample was kept at room temperatureunder stirring, 14.6 ml toluene solution (0.001029 mmol/ml) of component(a2-172) below was added dropwise thereto over 20 minutes. After themixture was stirred for 1 hour, the solids were collected by filtrationand washed sufficiently with toluene, and 50 ml purified decane wasadded thereto to give a decane slurry of component (b2-1-a2-195).

A part of this slurry was collected to analyze its concentration,indicating 1.26 mg/mL magnesium and 29.0 μg/mL zirconium. Accordingly,the content of zirconium atom in 1 g of the component (b2-1-a2-172) wascalculated to be 4.1 mg/g.

Polymerization

Polymerization was carried out in the same manner as in Example 12except that in the Polymerization in Example 12, the component(b2-1-a2-172) prepared above was used in place of the component(b1-1-a2-195). As a result, 55.9 g polyethylene was obtained.

The polymerization activity was 159.7 kg/mmol-Zr·hr, and thepolymerization activity per g of the component (b2-1-a2-172) was 7.2kg/g-cat·hr, and this polyethylene had a [η] value of 17.2 dl/g and abulk density of 0.29 g/cm³.

Example 13

Preparation of Component (b1-3)

A flask having an internal volume of 200 mL purged sufficiently withnitrogen was charged with 25 mL component (b1) (25 mmol in terms ofmagnesium atom) and 100 mL purified toluene, and while the temperatureof the solution was kept at −20° C. under stirring, 26 mmol triethylaluminum diluted with toluene was added dropwise thereto over 30minutes. Thereafter, the temperature of the solution was increased to80° C. over 130 minutes, and the mixture was reacted for 1 hour. Whilethe temperature was kept at 80° C., 250 mmol triethyl aluminum dilutedwith toluene was again added dropwise thereto over 30 minutes, and themixture was further reacted under heating for 1 hour. After the reactionwas finished, the solids were collected by filtration and washedsufficiently with toluene, and 100 mL toluene was added thereto to forma toluene slurry of component (b1-3). The average particle diameter ofthe resulting component (b1-3) was 11 μm.

A part of the component (b1-3) prepared by the above procedure was driedand examined for its composition, indicating 25.0 weight % magnesium,0.6 weight % aluminum, 2.6 weight % 2-ethylhexoxy group and 71.0 weight% chlorine. Accordingly, the molar ratio of magnesium to aluminum(Mg/Al) was 46.3, and the molar ratio of 2-ethylhexoxy group to aluminum(OR/Al) was 0.9.

Preparation of Component (b1-3-a2-172)

A flask having an internal volume of 200 ml purged sufficiently withnitrogen was charged with purified toluene so as to adjust the totalvolume to 85.3 mL and with component (b1-3) in an amount of 3 mmol interm of magnesium atom. While the sample was kept at 25° C. understirring, 14.7 mL toluene solution (0.001021 mmol/ml) of component(a2-172) below was added dropwise thereto over 20 minutes. After themixture was stirred for 1 hour, the solids were collected by filtrationand washed sufficiently with toluene, and decane was added thereto togive a decane slurry of component (b1-3-a2-172).

A part of this slurry was collected to analyze its concentration,indicating 1.05 mg/mL magnesium and 24.0 μg/mL zirconium. Accordingly,the content of zirconium atom in 1 g of the component (b1-3-a2-172) wascalculated to be 5.72 mg/g.

Polymerization

Polymerization was carried out in the same manner as in Example 12except that in the Polymerization in Example 12, the component(b1-3-a2-172) prepared above was used in place of the component(b1-1-a2-195). As a result, 37.8 g polyethylene was obtained.

The polymerization activity was 108.1 kg/mmol-Zr·hr, and thepolymerization activity per g of the component (b1-3-a2-172) was 6.8kg/g-cat·hr, and this polyethylene had a [η] value of 16.6 dl/g and abulk density of 0.40 g/cm³.

Example 14

Preparation of Component (b1-4)

A flask having an internal volume of 200 mL purged sufficiently withnitrogen was charged with 25 mL component (b1) (25 mmol in terms ofmagnesium atom) prepared in Example 1 and with 100 mL anhydrous1,2-dichlorobenzene, and while the temperature of the solution was keptat 0° C. under stirring, 26 mmol triethyl aluminum diluted withanhydrous 1,2-dichlorobenzene was added dropwise thereto over 30minutes. Thereafter, the temperature of the solution was increased to80° C. over 150 minutes, and the mixture was reacted for 1 hour. Whilethe temperature was kept at 80° C., 175 mmol triethyl aluminum dilutedwith anhydrous 1,2-dichlorobenzene was again added dropwise thereto over30 minutes, and the mixture was further reacted under heating for 1hour. After the reaction was finished, the solids were collected byfiltration and washed sufficiently with toluene, and 100 mL toluene wasadded thereto to form a toluene slurry of component (b1-4). The averageparticle diameter of the resulting component (b1-4) was 8 μm.

A part of the component (b1-4) prepared by the above procedure was driedand examined for its composition, indicating 24.0 weight % magnesium,0.6 weight % aluminum, 4.8 weight % 2-ethylhexoxy group and 68.0 weight% chlorine. Accordingly, the molar ratio of magnesium to aluminum(Mg/Al) was 44.4, and the molar ratio of 2-ethylhexoxy group to aluminum(OR/Al) was 1.66.

Preparation of Component (b1-4-a2-172)

A flask having an internal volume of 200 ml purged sufficiently withnitrogen was charged with purified toluene and component (b1-4) in anamount of 3 mmol in term of magnesium atom, so as to adjust the totalvolume to 85.2 mL. While the sample was kept at 25° C. under stirring,14.8 mL toluene solution (0.001014 mmol/mL) of the component (a2-172)used in Example 1 was added dropwise thereto over 20 minutes. After themixture was stirred for 1 hour, the solids were collected by filtrationand washed sufficiently with toluene, and decane was added thereto togive a decane slurry of component (b1-4-a2-172).

A part of this slurry was collected to analyze its concentration,indicating 1.21 mg/mL magnesium and 30.2 μg/mL zirconium. Accordingly,the content of zirconium atom in 1 g of the component (b1-4-a2-172) wascalculated to be 6.01 mg/g.

Polymerization

Polymerization was carried out in the same manner as in Example 12except that in the Polymerization in Example 12, the component(b1-4-a2-172) prepared above was used in place of the component(b1-1-a2-195). As a result, 70.3 g polyethylene was obtained.

Accordingly, the polymerization activity was 200.8 kg/mmol-Zr·hr, andthe polymerization activity per g of the component (b1-2-a2-172) was13.2 kg/g-cat·hr, and this polyethylene had a [η] value of 16.2 dl/g anda bulk density of 0.34 g/cm³.

Example 15

Preparation of Component (b1-5)

A flask having an internal volume of 400 mL purged sufficiently withnitrogen was charged with 25 mL component (b1) (25 mmol in terms ofmagnesium atom) prepared in Example 1 and 100 mL purified toluene, andwhile the temperature of the solution was kept at 0° C. under stirring,13 mmol triethyl aluminum diluted with toluene was added dropwisethereto over 15 minutes. Thereafter, the temperature of the solution wasincreased to 105° C. over 110 minutes, and the mixture was reacted for 2hours. Then, this reaction solution was cooled to −20° C., and while thetemperature of the solution was kept at −20° C. under cooling, 13 mmoltriethyl aluminum diluted with toluene was again added dropwise theretoover 15 minutes. Thereafter, the temperature of the solution wasincreased to 105° C. over 200 minutes, and the mixture was reacted for 1hour. Thereafter, the reaction mixture was cooled again to −20° C., andcharged with 13 mmol triethyl aluminum in the same manner as in theabove procedure, and the temperature of the mixture was increased to105° C. After the mixture was reacted at 105° C. for 1 hour, 162 mmoltriethyl aluminum diluted with toluene was added dropwise thereto over30 minutes, and the mixture was reacted for additional 1 hour underheating. After the reaction was finished, the solids were collected byfiltration and washed sufficiently with toluene, and 100 mL toluene wasadded thereto to form a toluene slurry of component (b1-5). The averageparticle diameter of the resulting component (b1-5) was 16 μm.

A part of the component (b1-5) prepared by the above procedure was driedand examined for its composition, indicating 26.0 weight % magnesium,0.4 weight % aluminum, 0.6 weight % 2-ethylhexoxy group and 72.0 weight% chlorine. Accordingly, the molar ratio of magnesium to aluminum(Mg/Al) was 72.2, and the molar ratio of 2-ethylhexoxy group to aluminum(OR/Al) was 0.31.

Preparation of Component (b1-5-a2-172)

A flask having an internal volume of 200 mL purged sufficiently withnitrogen was charged with purified toluene and component (b1-5) in anamount of 3 mmol in term of magnesium atom, so as to adjust the totalvolume to 85.5 mL. While the sample was kept at 25° C. under stirring,14.5 mL toluene solution (0.001032 mmol/ml) of the component (a2-172)used in Example 1 was added dropwise thereto over 20 minutes. After themixture was stirred for 1 hour, the solids were collected by filtrationand washed sufficiently with toluene, and decane was added thereto togive a decane slurry of component (b1-5-a2-172).

A part of this slurry was collected to analyze its concentration,indicating 1.30 mg/mL magnesium and 28.4 μg/mL zirconium. Accordingly,the content of zirconium atom in 1 g of the component (b1-5-a2-172) wascalculated to be 5.67 mg/g.

Polymerization

Polymerization was carried out in the same manner as in Example 10except that in the Polymerization in Example 10, the component(b1-5-a2-172) prepared above was used in place of the component(b1-1-a2-195). As a result, 53.1 g polyethylene was obtained.

Accordingly, the polymerization activity was 151.6 kg/mmol-Zr·hr, andthe polymerization activity per g of the component (b1-5-a2-172) was 9.4kg/g-cat·hr, and this polyethylene had a [η] value of 16.4 dl/g and abulk density of 0.37 g/cm³.

Example 16

Preparation of Component (b1-6)

A flask having an internal volume of 200 ml purged sufficiently withnitrogen was charged with 25 ml component (b1) (25 mmol in terms ofmagnesium atom) and 100 ml anhydrous 1,2-dichlorobenzene, and while thetemperature of the solution was kept at 15° C. under stirring, 26 mmoltriethyl aluminum diluted with purified decane was added dropwisethereto over 30 minutes. Thereafter, the temperature of the solution wasincreased to 80° C. over 120 minutes, and the mixture was reacted foradditional 60 minutes. While the temperature was kept at 80° C., 49 mmoltriethyl aluminum diluted with purified decane was again added dropwisethereto over 30 minutes, and the mixture was further reacted underheating for 60 minutes. After the reaction was finished, the solids werecollected by filtration and washed sufficiently with toluene, and 50 mltoluene was added thereto to form a toluene slurry of component (b1-6).The average particle diameter of the resulting component (b1-6) was 7μm.

A part of the component (b1-6) prepared by the above procedure was driedand examined for its composition, indicating 19.0 weight % magnesium,2.5 weight % aluminum, 19.1 weight % 2-ethylhexoxy group and 54.0 weight% chlorine. Accordingly, the molar ratio of magnesium to aluminum(Mg/Al) was 8.4, and the molar ratio of 2-ethylhexoxy group to aluminum(OR/Al) was 1.6.

Preparation of Component (b1-6-a2-172)

A flask having an internal volume of 200 mL purged sufficiently withnitrogen was charged with purified toluene and component (b1-6) in anamount of 3 mmol in term of magnesium atom, so as to adjust the totalvolume to 85.3 mL. While the sample was kept at 25° C. under stirring,14.7 mL toluene solution (0.001018 mmol/mL) of the component (a2-172)used in Example 1 was added dropwise thereto over 20 minutes. After themixture was stirred for 1 hour, the solids were collected by filtrationand washed sufficiently with toluene, and decane was added thereto togive a decane slurry of component (b1-6-a2-172).

A part of this slurry was collected to analyze its concentration,indicating 1.30 mg/mL magnesium and 28.4 μg/mL zirconium. Accordingly,the content of zirconium atom in 1 g of the component (b1-6-a2-172) wascalculated to be 5.67 mg/g.

Polymerization

Polymerization was carried out in the same manner as in Example 10except that in the Polymerization in Example 10, the component(b1-6-a2-172) prepared above was used in place of the component(b1-1-a2-195). As a result, 60.5 g polyethylene was obtained.

Accordingly, the polymerization activity was 173.0 kg/mmol-Zr·hr, andthe polymerization activity per g of the component (b1-6-a2-172) was 9.8kg/g-cat·hr, and this polyethylene had a [α]value of 17.2 dl/g and abulk density of 0.22 g/cm³.

Example 17

Preparation of Component (b1-7)

Component (b1-7) was prepared in the same manner as in Example 19 exceptthat in the Preparation of component (b1-6) in Example 19, chlorobenzenewas used in place of anhydrous 1,2-dichlorobenzene.

The average particle diameter of the prepared component (b1-7) was 5 μm,and a part thereof was dried and examined for its composition,indicating 18.0 weight % magnesium, 2.6 weight % aluminum, 20.4 weight %2-ethylhexoxy group and 52.0 weight % chlorine. Accordingly, the molarratio of magnesium to aluminum (Mg/Al) was 7.7, and the molar ratio of2-ethylhexoxy group to aluminum (OR/Al) was 1.6.

Preparation of Component (b1-7-a2-172)

A flask having an internal volume of 200 mL purged sufficiently withnitrogen was charged with purified toluene and component (b1-7) in anamount of 3 mmol in term of magnesium atom, so as to adjust the totalvolume to 85.7 mL. While the sample was kept at 25° C. under stirring,14.3 ml toluene solution (0.001047 mmol/mL) of the component (a2-172)used in Example 1 was added dropwise thereto over 20 minutes. After themixture was stirred for 1 hour, the solids were collected by filtrationand washed sufficiently with toluene, and decane was added thereto togive a decane slurry of component (b1-7-a2-172).

A part of this slurry was collected to analyze its concentration,indicating 1.30 mg/mL magnesium and 28.4 μg/mL zirconium. Accordingly,the content of zirconium atom in 1 g of the component (b1-7-a2-172) wascalculated to be 5.67 mg/g.

Polymerization

Polymerization was carried out in the same manner as in Example 10except that in the Polymerization in Example 10, the component(b1-7-a2-172) prepared above was used in place of the component(b1-1-a2-195). As a result, 58.6 g polyethylene was obtained.

Accordingly, the polymerization activity was 167.5 kg/mmol-Zr·hr, andthe polymerization activity per g of the component (b1-7-a2-172) was 8.4kg/g-cat·hr, and this polyethylene had a [η] value of 18.1 dl/g and abulk density of 0.23 g/cm³.

Example 18

Preparation of Component (b3)

95.2 g (1.0 mole) anhydrous magnesium chloride, 582 ml anhydrous1,2-dichlorobenzene and 306.0 g (2.35 moles) 2-ethylhexyl alcohol werereacted at 130° C. for 2 hours to give a uniform solution?? (component(b3)).

Preparation of Component (b3-1)

A flask having an internal volume of 200 mL purged sufficiently withnitrogen was charged with 25 mL component (b3) (25 mmol in terms ofmagnesium atom) and 100 mL anhydrous 1,2-dichlorobenzene, and while thetemperature of the solution was kept at 0° C. under stirring, 26 mmoltriethyl aluminum diluted with anhydrous 1,2-dichlorobenzene was addeddropwise thereto over 30 minutes. Thereafter, the temperature of thesolution was increased to 100° C. over 200 minutes, and the mixture wasreacted for 1 hour. While the temperature was kept at 100° C., 175 mmoltriethyl aluminum diluted with anhydrous 1,2-dichlorobenzene was againadded dropwise thereto over 30 minutes, and the mixture was furtherreacted under heating for 1 hour. After the reaction was finished, thesolids were collected by filtration and washed sufficiently withtoluene, and 100 mL toluene was added thereto to form a toluene slurryof component (b3-1). The average particle diameter of the resultingcomponent (b3-1) was 4 μm.

A part of the component (b3-1) prepared by the above procedure was driedand examined for its composition, indicating 26.0 weight % magnesium,0.4 weight % aluminum, 4.8 weight % 2-ethylhexoxy group and 68.0 weight% chlorine. Accordingly, the molar ratio of magnesium to aluminum(Mg/Al) was 72.2, and the molar ratio of 2-ethylhexoxy group to aluminum(OR/Al) was 0.3.

Preparation of Component (b3-1-a2-172)

A flask having an internal volume of 200 mL purged sufficiently withnitrogen was charged with purified toluene and component (b3-1) in anamount of 3 mmol in term of magnesium atom, so as to adjust the totalvolume to 85.4 ml. While the sample was kept at 25° C. under stirring,14.5 mL toluene solution (0.001022 mmol/mL) of the component (a2-172)used in Example 1 was added dropwise thereto over 20 minutes. After themixture was stirred for 1 hour, the solids were collected by filtrationand washed sufficiently with toluene, and 50 mL decane was added theretoto give a decane slurry of component (b3-1-a2-172).

A part of this slurry was collected to analyze its concentration,indicating 1.29 mg/mL magnesium and 30.9 μg/mL zirconium. Accordingly,the content of zirconium atom in 1 g of the component (b3-1-a2-172) wascalculated to be 6.23 mg/g.

Polymerization

Polymerization was carried out in the same manner as in Example 10except that in the Polymerization in Example 10, the component(b3-1-a2-172) prepared above was used in place of the component(b1-1-a2-195). As a result, 108.0 g polyethylene was obtained.

Accordingly, the polymerization activity was 308.4 kg/mmol-Zr·hr, andthe polymerization activity per g of the component (b3-1-a2-172) was21.0 kg/g-cat·hr, and this polyethylene had a [η] value of 17.9 dl/g anda bulk density of 0.22 g/cm³.

Example 19

Preparation of Component (b3-2)

A flask having an internal volume of 200 mL purged sufficiently withnitrogen was charged with 25 mL component (b3) (25 mmol in terms ofmagnesium atom) and 100 mL toluene, and while the temperature of thesolution was kept at −20° C. under stirring, 26 mmol triethyl aluminumdiluted with toluene was added dropwise thereto over 30 minutes.Thereafter, the temperature of the solution was increased to 100° C.over 320 minutes, and the mixture was reacted for 1 hour. While thetemperature was kept at 100° C., 175 mmol triethyl aluminum diluted withtoluene was again added dropwise thereto over 30 minutes, and themixture was further reacted under heating for 1 hour. After the reactionwas finished, the solids were collected by filtration and washedsufficiently with toluene, and 100 mL toluene was added thereto to forma toluene slurry of component (b3-2). The average particle diameter ofthe resulting component (b3-2) was 6 μm.

A part of the component (b3-2) prepared by the above procedure was driedand examined for its composition, indicating 2.6.0 weight % magnesium,0.4 weight % aluminum, 0.7 weight % 2-ethylhexoxy group and 19.0 weight% chlorine. Accordingly, the molar ratio of magnesium to aluminum(Mg/Al) was 72.2, and the molar ratio of 2-ethylhexoxy group to aluminum(OR/Al) was 0.4.

Preparation of Component (b3-2-a2-172)

A flask having an internal volume of 200 mL purged sufficiently withnitrogen was charged with purified toluene and component (b3-2) in anamount of 3 mmol in term of magnesium atom, so as to adjust the totalvolume to 85.2 mL. While the sample was kept at 25° C. under stirring,14.8 mL toluene solution (0.001011 mmol/mL) of the component (a2-172)used in Example 1 was added dropwise thereto over 20 minutes. After themixture was stirred for 1 hour, the solids were collected by filtrationand washed sufficiently with toluene, and decane was added thereto togive a decane slurry of component (b3-2-a2-172).

A part of this slurry was collected to analyze its concentration,indicating 1.05 mg/mL magnesium and 24.7 μg/mL zirconium. Accordingly,the content of zirconium atom in 1 g of the component (b3-2-a2-172) wascalculated to be 6.12 mg/g.

Polymerization

Polymerization was carried out in the same manner as in Example 10except that in the Polymerization in Example 10, the component(b3-2-a2-172) prepared above was used in place of the component(b1-1-a2-195). As a result, 82.9 g polyethylene was obtained.

Accordingly, the polymerization activity was 236.7 kg/mmol-Zr·hr, andthe polymerization activity per g of the component (b3-2-a2-172) was15.8 kg/g-cat·hr, and this polyethylene had a [η] value of 17.4 dl/g anda bulk density of 0.23 g/cm³.

Example 20

Preparation of Component (b3-3)

A flask having an internal volume of 400 mL purged sufficiently withnitrogen was charged with 12.5 mL component (b3) (25 mmol in terms ofmagnesium atom) and 250 mL toluene, and while the temperature of thesolution was kept at −20° C. under stirring, 10.2 mmol triethyl aluminumdiluted with toluene was added dropwise thereto over 30 minutes.Thereafter, the temperature of the solution was increased to 100° C.over 1160 minutes, and the mixture was reacted for 1 hour. While thetemperature was kept at 100° C., 87.5 mmol triethyl aluminum dilutedwith toluene was again added dropwise thereto over 30 minutes, and themixture was further reacted under heating for 1 hour. After the reactionwas finished, the solids were collected by filtration and washedsufficiently with toluene, and 100 mL toluene was added thereto to forma toluene slurry of component (b3-3). The average particle diameter ofthe resulting component (b3-3) was 5 μm.

A part of the component (b3-3) prepared by the above procedure was driedand examined for its composition, indicating 24.0 weight % magnesium,0.4 weight % aluminum, 0.8 weight % 2-ethylhexoxy group and 69.0 weight% chlorine. Accordingly, the molar ratio of magnesium to aluminum(Mg/Al) was 66.6, and the molar ratio of 2-ethylhexoxy group to aluminum(OR/Al) was 0.4.

Preparation of Component (b3-3-a2-172)

A flask having an internal volume of 200 mL purged sufficiently withnitrogen was charged with purified toluene and component (b3-3) in anamount of 3 mmol in term of magnesium atom, so as to adjust the totalvolume to 85.7 mL. While the sample was kept at 25° C. under stirring,14.3 mL toluene solution (0.001052 mmol/mL) of the component (a2-172)used in Example 1 was added dropwise thereto over 20 minutes. After themixture was stirred for 1 hour, the solids were collected by filtrationand washed sufficiently with toluene, and decane was added thereto togive a decane slurry of component (b3-3-a2-172).

A part of this slurry was collected to analyze its concentration,indicating 1.26 mg/mL magnesium and 28.3 μg/mL zirconium. Accordingly,the content of zirconium atom in 1 g of the component (b3-3-a2-172) wascalculated to be 5.39 mg/g.

Polymerization

Polymerization was carried out in the same manner as in Example 10except that in the Polymerization in Example 10, the component(b3-3-a2-172) prepared above was used in place of the component(b1-1-a2-195). As a result, 99.5 g polyethylene was obtained.

Accordingly, the polymerization activity was 284.3 kg/mmol-Zr·hr, andthe polymerization activity per g of the component (b3-3-a2-172) was16.8 kg/g-cat·hr, and this polyethylene had a [η] value of 22.0 dl/g anda bulk density of 0.22 g/cm³.

Comparative Example 1

Preparation of Component (b1-8)

A flask having an internal volume of 200 ml purged sufficiently withnitrogen was charged with 25 ml component (B1) (25 mmol in terms ofmagnesium atom) and 100 ml purified decane, and while the temperature ofthe solution was kept at 15° C. under stirring, 26 mmol triethylaluminum diluted with purified decane was added dropwise thereto over 30minutes. Thereafter, the temperature of the solution was increased to80° C. over 2 hours, and the mixture was reacted for 1 hour. After thereaction was finished, the solids were collected by filtration andwashed sufficiently with toluene, and 100 ml toluene was added theretoto form a toluene slurry of component (b1-8). The average particlediameter of the resulting component (b1-8) was 20 μm.

A part of the component (component (b1-8)) prepared by the aboveprocedure was dried and examined for its composition, indicating 6.5weight % magnesium, 3.5 weight % aluminum, 78.0 weight % 2-ethylhexoxygroup and 18.0 weight % chlorine, and the molar ratio of magnesium toaluminum (Mg/Al) was 2.0, and the molar ratio of 2-ethylhexoxy group toaluminum (OR/Al) was 4.6.

Preparation of Component (b1-8-a2-1)

A flask having an internal volume of 200 ml purged sufficiently withnitrogen was charged with component (b1-8) in an amount of 10 mmol interms of magnesium atom and 100 ml purified toluene, and while thetemperature of the solution was kept at room temperature under stirring,50 ml toluene solution (0.001 mmol/ml) of component (a2-1) below wasadded dropwise thereto over 20 minutes. After the mixture was stirredfor 1 hour, the solids were collected by filtration (component(b1-1-a2-1)). A part of the component (b1-1-a2-1) prepared by the aboveprocedure was dried and examined for its composition, revealing that thecomponent (a2-1) was hardly contained (0.004 weight %).

Comparative Example 2

500 ml purified toluene was introduced into an SUS autoclave having aninternal volume of 1 liter purged sufficiently with nitrogen, and theliquid phase and gaseous phase were saturated with ethylene by blowingethylene. Thereafter, the toluene was heated to 75° C., and theautoclave was charged in an ethylene stream with 1.9 mmol triisobutylaluminum and 0.5 ml component (b1) (0.5 mmol in terms of magnesium atom)prepared in the same manner as in Example 1, and the mixture was reactedfor 15 minutes, to prepare a magnesium-containing carrier component (B)in the system. Then, the autoclave was charged with component (a2-116),0.384 mg (0.0005 mmol in terms of zirconium atom), and polymerizationwas carried out for 15 minutes at an ethylene pressure of 0.8 MPa·G.During the polymerization, the system was kept at 75° C. and at anethylene pressure of 0.8 MPa·G. After the polymerization was finished,the reaction product was introduced into a large amount of methanol toprecipitate the whole polymer, and after hydrochloric acid was added,the polymer was collected with a glass filter. The resulting polymer wasdried under vacuum for 10 hours to give 33.25 g polyethylene. The [η]value of this polyethylene was 15.8 dl/g.

The polymerization activity per molecule of the component (a2-116) wasas high as 266,000 g/mmol-Zr·hr, but the activity of 1 g startingmaterial used in preparation of the carrier component (B) was as verylow as 0.2 kg/g-cat·hr, and the bulk density was also as low as 0.09g/cm³.

The calculated molar ratio of magnesium to aluminum (Mg/Al) in thesystem was 0.26, and the calculated molar ratio of 2-ethylhexoxy groupto aluminum (OR/Al) was 0.79. Separately, the carrier component (B) wasprepared in the same method as described above, and its measuredparticle diameter was 1 μm or less.

INDUSTRIAL APPLICABILITY

The present invention is industrially useful because an olefin polymerexcellent in powdery properties can be obtained by an extremely highpolymerization activity even without combination with an expensiveorganoaluminum oxy compound or organoboron compound.

1. A carrier component suitable as an olefin polymerization catalyst,which is insoluble in a hydrocarbon solvent, is in the form of solidfine particles having an average particle diameter of 3 to 80 μm, andcontains a magnesium atom, an aluminum atom and a C₁₋₂₀ alkoxy groupsimultaneously, wherein the molar ratio of magnesium atom to aluminumatom (Mg/Al) is in the range of 1.0 to 300, and the molar ratio ofalkoxy group to aluminum atom (alkoxy group/Al) is in the range of 0.05to 2.0.
 2. The carrier component according to claim 1, wherein the molarratio of magnesium atom to aluminum atom (Mg/Al) is in the range of 40to 150, and the molar ratio of alkoxy group to aluminum atom (alkoxygroup/Al) is in the range of 0.2 to 2.0.
 3. The carrier componentaccording to claim 1, which is obtained by contacting a magnesium halidewith a C₁₋₂₀ alcohol and then contacting the product with anorganoaluminum compound represented by the general formula (Z):AlR_(n)X_(3-n)  (Z) wherein R represents a C₁₋₂₀ hydrocarbon group, Xrepresents a halogen atom or a hydrogen atom, n is an integer of 1 to 3,and when there are a plurality of Rs, Rs may be the same or different,and when there are a plurality of Xs, Xs may be the same or different.4. An olefin polymerization catalyst comprising the carrier componentdescribed in claim
 1. 5. An olefin polymerization catalyst comprising:(A) a transition metal compound from any one of groups 3 to 11 in theperiodic table, having a ligand containing two or more atoms selectedfrom a boron atom, a nitrogen atom, an oxygen atom, a phosphorus atomand a sulfur atom, (B) a carrier component suitable as an olefinpolymerization catalyst, which is insoluble in a hydrocarbon solvent, isin the form of solid fine particles having an average particle diameterof 3 to 80 μm, and contains a magnesium atom, an aluminum atom and aC₁₋₂₀ alkoxy group simultaneously, wherein the molar ratio of magnesiumatom to aluminum atom (Mg/Al) is in the range of 1.0 to 300, and themolar ratio of alkoxy group to aluminum atom (alkoxy group/Al) is in therange of 0.05 to 2.0, and (C) a specific organometallic compounds, ifnecessary.
 6. The olefin polymerization catalyst according to claim,wherein the transition metal compound (A) is carried on the carriercomponent (B).
 7. A polyolefin having a bulk density of 0.20 (g/cm³) ormore, which is obtained by homopolymerizing or copolymerizing an olefinin the presence of the olefin polymerization catalyst described in claim4.
 8. The olefin polymerization catalyst according to claim 5, whereinthe molar ratio of magnesium atom to aluminum atom (Mg/Al) is in therange of 40 to 150, and the molar ratio of alkoxy group to aluminum atom(alkoxy group/Al) is in the range of 0.2 to 2.0.
 9. The olefinpolymerization catalyst according to claim 5, which is obtained bycontacting a magnesium halide with a C₁₋₂₀ alcohol and then contactingthe product with an organoaluminum compound represented by the generalformula (Z):AlR_(n)X_(3-n)  (Z) wherein R represents a C₁₋₂₀ hydrocarbon group, Xrepresents a halogen atom or a hydrogen atom, n is an integer of 1 to 3,and when there are a plurality of Rs, Rs may be the same or different,and when there are a plurality of Xs, Xs may be the same or different.